opment of spore-forming bacteria, which in the past have caused spoilage in various food products. Where such a blend is pasteurized, temperatures required for killing bacteria are approximately 10" F.lower than in the case of nonacidified juices (Table IV). Further, it should be noted that spore-forming bacteria are not entirely killed in juices, whether or not they are acidified, The important difference, o ow ever, lies in the inability of the organisms to grow in the acidified juice. Curves show that pasteurization can be conducted at much lower temperatures than 18&B90" E'. The data indicate thia, but spoilage types, such as lactic acid bacteria, are present in relatively low numbers, and heating to approximately 165" F. is required for complete killing. The amount of acid necessary to obtain biends with a hydrogen-ion concentration of pH 4.0-4.1 varies considerably, not only with the vegetable used but also between different samples of a single vegetable (Table V). The quantity of kraut juice to obtain a pH of 4.00 varies from 37.2 to 69.8 cc, for celery juice, 28.6 to 164.8 cc, for carrot juice, and 28.6 to 170.8 cc. for all juices. The blends of sauerkraut juice with vegetable juices have, in general, been far more appetizing than the straight vegetable juices. Furthermore, they may be blended with tomato juice in various proportions to produce pleasing tomato juice cocktails. Celery, carrot, beet, and turnip blends have been particularly satisfactory. Juices have ordinarily been extracted from the fresh vegetable; and if the blend could not be prepared immediately, the juice was rapidly heated to 185-190" F. in order to inactivate the enzymes m-hich wouid quickly cause a change in flavor, co1or, a,nd vitamin content. Blanching previous to extraction may inactivate the enzymes more rapidly, but thia treatment changes the character of the vegetable so much that the estracted juices are not so satisfactory. Flash pasteurization a t 185--190"E'. preceded by deaeration, filling into bottles or cans a t the above temperature, folloxed by cooling after 5 minutes has been found to be a n effective means of preserving these blends without changing their flavor. The same equipment used for fruit juices (Figure 2) is satisfactory for the deaeration and flash pasteurization of either acidified vegetable juices or blends of vegetable juices with sauerkraut or rhubarb juice.
1936. (19) Weslern Cunner and Packer, Yearbook, 1942. .APPROVED by t h e Dirootor, New York 8 t a t e Agricultural Experiment Station. %ospublication as Journal Paper 524.
,
E: PARK
Beatrice Creamery Comyanp, Chicago, I)!
Acknowledgment The authors wish to thank Harry lVmBlock foe carrying out the tin and iron analyses and Katherine A. Kheeler for the ascorbic acid deterininatjons seport,ed in this paper.
Literature cite Ayers, 8. H., F r u i t Products J , , 17, 41 (1.937). I b i d . , 21, 227 (1942). Beattie, H. G., and Pederson, C . 8.Beavens, E . A., and B e a t t i e , H. G., C a n n e l , 94, No. 21, 15 11942'1 Ch'ace, E. &I.$ Calif. C i t ~ o y r a p h 5, , 261 (1920). Cruess, W.V., a n d Celmer, R., W e s t e r n Canner and Packer, 30, I
No. 5, 43 (1938). Cruess, W. V., and Chong, G., C a n n e r , 93, No. 26, . I 1 (1941). Cruess, W.V., Thomas, W.B., and Celmer, R., Ibid., 85, No. 3 . 9 (1937). Cruess, W. V., and Yerman, F.,Fruit Products J.,17,9 (1937). Graham, W. E., Canning A g e , 21, 522 (1940). Heid, J. L., a n d Scott, W. C . , Fruit Products J.,16, 136 (1937). Ibid.,17, 100 (1937). Marsh, G. L., C a n n e r , 95, KO. 9, 7 (1942). M o t t e r n , H. H., and Loesecke, El. W. von, Fruit Products J.. 12, 326 (1933) Pederson, C , S.,B e a t t i e , H . G., and Beavens, E. d., Ibid., 20, 227 (1941). Pederson, C . S., Beattie, H. G., and Beavens, E. A , . Proc. Inst. Food Technologists, 2, 75 (1941). Pederson, C. S., a n d Tressler, D. K., 1x11.ENG.CEIEM.,30,964
(1938).
ERETOFORE the intelligent application of cleaning agents has involved a consideration of certain primary and secondary factors. The primary factors have been concerned with the chemical character of the water supply used in the cleaning operations as well as the degree and type of uncleanliness of the equipment. The secondary factors have implicated the availability of the alkalinity of the detergent used, the temperature and period of exposure, the proper application oi the cleaning solution, and the thoroughness of applied mechanical action. Alkalies and alkaline buffer salts have been almost exclusively used as detergents for several reasons. First and
January, 1943
INDUSTRIAL AND ENGINEERING CHEMISTRY
foremost from the standpoint of public health, they are nontoxic. They are also effective detergents although they do vary in their emulsifying, peptizing, wetting, and dispersive properties; for example, trisodium phosphate is superior to soda ash as an emulsifier of milk fat and peptizer of protein, while the poly-phosphates are not only superior to both, as regards such characteristics, but have wetting and dispersive properties lacking in the other two alkalies Recent developments, however, have indicated that alkalies can no longer claim pre-eminence as effective detergents. I n fact, in the light of more modern knowledge there is much evidence to suggest that alkaline compounds are responsible for many of the quality failures in present-day sanitary practice. An illustration occurs in can washing; there is an overwhelming abundance of evidence to indicate that the familiar 5-, 8-, and 10-gallon milk or cream can is most frequently a source of serious and far-reaching quality defections in a variety of dairy products. Investigation has revealed that most mechanically cleaned cans have an unmistakable inoculation of proteolytic and oxidizing types of bacteria, and that such microorganisms are found most abundantly in the cans cleaned last in the day's run whenever alkaline cleaning compounds were used. Further studies indicate that these bacteria were being developed in the cleaning solution in spite.of temperatures as high as 170" F. and a definite alkalinity as strong as 0.25 per cent
101
Table I. Effect of Acid Reaction on Cleaned Cream Cans Rinsed w i t h Steam Acidified w i t h Citric Acid Can No." 5 6 7 ' S 9
Can Reaction Acidb Acidb AlkalineC Alkalinec Acidb Alkalined Cleaning soln. 6
Bacterial Count Standard plate Proteolytic 80 30 60 30 360 190 270 80 3 0 35 2 I f
Colony Reaction Acid Alkaline 50 30 30 30 20 340 0 0
270
3 0 35 Apparently all alkaline Rinse water e 180 15 35 145 a Cans 9 and 11 were tested a t the start of the day's r u n ; cans 5 6 7, and 8 were tested later, after operations had been underway for a few hdurk b Sweet odor in moist can held overnight. C Putrid odor in moist can held overnight. d Dirty unclean odor in can held overnight. e Sample taken after cleaning 400 cans. f Too many bacteria colonies to count. 11
mains, as was repeatedly demonstrated by (a) no development of offensive odors in a moistened can, (b) a preponderance of acid types of bacteria in exhaustive microbial examinations of washed cans given this final acid rinse, and (c) the incidental reduction in the total numbers of bacteria originally present.
Rinsing with organic acids
In preliminary plant trials citric acid was used because it was the only organic acid with which we were sufficiently familiar a t the time to try out the original can acidification As the day's operation continues, sufficient protein actreatments. While it was known to be slightly corrosive, it cumulates in the can washer to increase the film-forming is not nearly so undesirable as the mineral acids in this reproperties of the cleaning solution. The film thus formed spect. A 0.5 per cent solution of citric acid was supplied to an appears to cling to the metal surface in spite of the subsequent ejector valve attached to the last steam .!et on the can washer. hot water and steam rinses and the hot air blasts. It also When the steam jet was retains the undesirable opened, the velocity of proteolytic bacteria and the steam sucked up the protein food material for acid solution and mixed the bacteria in sufficient it with the steam to concentration to make change the reaction of trouble if the can bethe steamed can from comes moistened before alkaline to acid. The it is again filled with amount of acid mixed milk or cream. I n fact, with the steam was consometimes even dry trolled by a valve in the cans inoculate the milk suction line. To see if with bacteria which imthe cans were properly part bitter and often a c i d i f i e d , a can was stale flavors to the fresh rinsed with 50 cc. of discream or milk poured tilled water, and the into them. reaction of the water Test runs showed that was determined coloristerilizing steam having metrically with bromoan acid reaction would thymol blue indicator. A correct this condition by reaction of pH 6.0 to 6.5 releasing the colloidal was found to beadequate. film of cleaning solution The comparative data with its bacterial conin Table I indicate that tamination and nutrients acidulating t h e s t e a m generally adhering to the with a citric acid solution metal surface of the can, sufficient t o change the by greatly increasing the reaction of cleaned cream sterilizing action of the cans from alkaline to steam itself, and by acid resulted not only in leaving the inner surface significant changes in the of the can in an acid types and numbers of the condition. The apparbacteria present but also ent effect of the treatin the odor of the treated Spraying Previously Cleansed Coil Pasteurizer Vat ment is that no apprecans. They were held with Acid Cleaner Solution (Replacing Chlorine Rinse ciable concentration of overnight after adding Solution) to Prevent Contamination b y Quality-Defecprotein material or pro100 cc. of sterile water five Microorganisms teolytic b a c t e r i a r e -
(as NazO).
*
INDUSTRIAL AND ENGINEERING CHEMISTRY
102
to moisten the inner surfaces. Incidentally, 1-cc. dilutions of the 100 cc. of sterile water used for checking the cleansed cans of both acid and alkaline reactions were plated immediately after their delivery from the can washer on standard tryptone-glucose extract-milk (T-G-E-M) agar and incubated for 48 hours a t 37" C. The plates were then counted and the totals reported as standard plate count. Colonies surrounded by a clear zone indicating proteolysis of the milk were reported as proteolytic count. The plates m r e then flooded with bromothymol blue indicator solution, and the reaction was noted and reported as numbers of acid or alkaline colonies. I n this manner general types were identified and reported. The bacteria in the solution appeared to be either proteoly.tic or alkali forming in spite of the p H 10 alkalinity and 140' F.temperature, The 170" F.rinse mater also showed R positive count of proteolytics and alkali formers, Table 11. Chemical Analysis of Cleaning S o I ~ t i in ~ nCan Washer during Operation (Per Cent) Sample
.4lkahiity (as N a O R )
Fresh solution After 320 cansn After 607 cansQ a Used for shipping
0.25
0.22 0.29 sour cream.
X i l k Fat 0.00 0.18 0.31
Protein 'rrace 0.03 0.18
Total Solids Ash 0 . 1 ~ 0 ii 0.54 0.20 0.74 0.16
Vol. 35, Ne. I
a variety of dairy plants with noticeable improvement in^ the quality of raw milk and cream transported in these mechanically cleaned cans. I n a special report of tlie Technical Committee of the Uairy Industry Supply Association (i?),i t was suggested that the acid rinsing of washed cans might tend to the development of careless production practice. Xothing could be farther from the original purposes of such a development, and clearly points to a common misconception d i i c h might be resolved whcn the microbiology and biochemistry of can washing and other similar dairy cleaning practices are ignored. It might be well to emphasize that the improvements in can washing during recent years are essentially the result of good engineering and hydraulics.
Alkaline washing Data were obtained after washing cans used for transport;iiig sour cream on a modern can washer, equipped with a n instrument designed to measure alkalinity in terms of its elect,rical resistance in order to ensure positive content of t,he cleaning solut'ion a t approximately 0,16 per cent (as Na20) when alkalies were used. I n Table III, A and 13, tlie cans were all washed with an alkaline solution; the alkali was compounded to embody t'he latest improvement in dispersive and emulsifying properties as \vel1 as the sulfonated alcohol netting agents. The particular alkaline product uscd has enabled many nat,ionally know1 dairy concerns with ex t,ensive research facilities to reduce the variety of cleaning conipourids needed for a mu1tiplicity of cleaning opera.tions, a t tremendous savings in operation. I n all instances, upondelivery from the c:m \rasher, thc inside surfaces of the cans were rinsed with 100 ml. of stmde water, and t,he rnoist>enedcans n-ere covered and held 48 hours a t room temperature. \i t the end of the 48-hour neriod the citnq \\-ere igairr i;horoughly rinser1 inside with 1- he same water before it K:LY pltatotl in 7'-G-E-M agar. Xi1 hamples \ T T J , ~ platcd i n tlriplicnte, aiitL tlit: total coiints and potcolytic: i 1 n c t e I: ia, co 111Its \Ycrc computod. One oi' t,hc tl l l 11 1 i c 11)1e pla tcs IVRS Nooticcl n-i t,li r (: i n o-.
After 400 cans liad been run through the vasher, the cleaning solution itself gave such a high bacterial count that an analysis was made of it a t different intervals during the day's run to see what chemical changes \\-ere taking place. The results are given in Table 11. Data in Table 11gives evidence that the accumulation of fat and protein increased n.ith the number of cream cans washed and provided nutrients for the surviving bacteria. The variations in alkalinity and ash can be explained on the basis of solution dissipation and dilution. Hoir.evcr, t,hemarked ini:rease in total solids, protein, and fat in the sample taken after cleaning 609 cans it-itli the tiecreases in allraliriity and :ish reported seem l o indicate that the milk fat c:r p r o t e i n complexes formed by reaction xith tlie alkali present contribute to colloitlai film formations in the cleaned cans. It' is true that the problem of corrosion has t o he met. By acidifying steam with suction injection of gluconic acid in coutrollable quantities, the can is given an acid r e a c t i o n of approximately pH 6,O t'o 6.5, n-ith no active corrosion Applying Acid Cleaner S ~ l u t i ~ asn a S p r a y t~ a Surface of the can. Subsequently C ~ ~ l eSubsequently r~ Cleaned with a Soff Bristle H a n d this method of acid rinsBrush ing has been tried in
f h c a,cid and a l k : i l i
Hoodecl wjth a, U.5 p o r cent aqueous so1i;ltion of 'r m e tli.v.l-p-~)lic~ri~l1 mine 11ydrorlilor,ide, according to met~fiocl of Ellingn-oi *1TcLcod,and Gor.tioii for t,lie purpose of counting the ositliziiig igpos of ba,cteria. 1T.e well recall the effectiveness of holding wnshed c m s with t h o sterile wa.t,er rinse for ttlir: 48-hour period hforc: plating to attest the c o n i p l e t e n c s s of the
INDUSTRIAL AND ENGINEERING CHEMISTRY
January, 1943
103
Table 111. Plate Counts on Tin-Coated Cans Washed by Various Methods and Then Rinsed with 100 M1. Sterile Water and Held 48 Hours at Room Temperature before Plating on T-G-E-M Agar Consecutive Can through Washer
Condition of Can
300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540
Good ' Good Good Rust spots on bottom Rust spots on bottom Poor, rust spots on bottom and neck Very poor, rusty Good Good Good
300 310 320 330 340 350 360 370 380 400 410 420 430 440 450 460 470 480 490 500 510 520 530 540
Good condition one soldered spot Poor condition,'rust spots Good condition Fair few rust spots Goo& condition Fair condition few bottom spots Good conditioh Few rust spots on bottom Good condition Good Good Good Very poor, bad bottom Good Rust lid, otherwise good Goodi Fair Food Good Fair, few tiny rust spots Fair. few tiny rust spots Good Good Good, rusty lid
210 220 230 240 250 300 330 340 380 410 420 430 440 450 460 47 0 500
Gnnd Good Fair, rust spots Fair. rust mots POO; rustyGood Good Very poor, rusty Fair, rust spots Fair, rust spots Fair, rust spots Good
Total Count
Proteolytic Types
Acid Types
A . Cans Washed with Alkali TNTCa 25,200,000 600,000 TNTC 800,000 9,000,000 TNTC TNTCa TNTCa TNTC 21,500 TNTC 48,000 9,000 TNTC 2,090 000 TNTC T ~ T C 1.000 400 TNTC 4,800 000 2,000,000 TNTC TNTC T ~ T C 400 1,000 5,000 2.000 400 3,000 TNTC 1,530,000 70,000 300 1,000 b 600 2,000 TNTC 810,000 150,000 3,500 1,000 9,000 TNTC 6,040,000 TNTC TNTC 30,000 1,610,000 TNTC TNTC 16,200,000 TNTC 9,000 72,000 TNTC 210,000 420,000 710 1,000 b 1,300 2,000 14,000 22,000 4,000
Y ;p
Alkali Types TNTCa TNTC TNTC TNTC TNTC 600 TNTC TNTC 600 1,800 3,000 700 TNTC 700 5,500 TNTC TNTC TNTC TNTC TNTC TNTC TNTC 300 700 8,000
Oxidizing Types
Odor
4,000 TNTC" TNTC TNTC TNTC TNTC TNTC 450 TNTC TNYC
Very bad Very bad Very bad Very bad Very bad Very bad Very bad Very bad Very bad Very bad Fair clean Good
800 TNTC 700 400 4,000 TNTC TNTC 630,000 TNTC TNTC 600
540 2,800
Fair Fair Bad Bad Bad Bad Bad Bad Bad Bad Bad Bad Bad
B. Alkali-Washed and Gluconio-Acid-Treated Cans
a b
En,+
--I-
Fair, rust spots Poor, rusty Poor, rusty Good
2,000 1,500 6,500 1,000 1 500 14:OOO 16,000 10,000 5,000 85,000 4,000 9.000 14,000 7,500 3 500 ( 1 ) 3:500 3,000,000 2,000 13 000 7:OOO 6,000 3,000 28,000 6,000
b b b Ir b b
2.000 b b b
b b b
8,000 13,000
I b b
b b
1,500 b b b
b
2.000 1,000 3,500 1,000 1,500 12,000 13,000 7,000 5,000 55,000
3,500 3,500 Few 2,000 1,000 7,000 5,000 3,000 20,000 6,000
C . Cans Washed with Mikro San Acid Cleaner b 1,100 1,500 b 150 200 b 400 400 b 100 100 b 1,500 2,000 b 1,500 1,600 b 200 200 1,200 12,500 4,000 300 300 b 300 300 b 5,000 6,000 b 400 200 b 2,500 3,000 b 2,000 4,000 b 5,900 11,000 b 500 500 b 6.000 6,500
2,000
b
500 3,000
b b b
b
b
3,000 3,000 3,000
5,000 2,000 5,000 2,000
30,000 4,000 1,000
3 000 3:OOO 4,000 3,000 3,000 3,000
1,000
7,500 b
TNYC
80,000
12'000
3,000 4,000 6,000 1,000 3,000 5,000
b
1,000
8,000
400 50
b b
b
b
b b
500 io0
500 b b
1,000 200 500
2,000 5,100 b
500
b
'
b b b b b b b b
1,500 b b
Good Good Good Good Good Good Good
clean clean clean clean clean clean clean
Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean Good clean
Too numerous to count. Less than 1 bacterium per ml. in rinse water after 48 hours.
cleaning method. For by such a method we demonstrated to one nationally known dairy equipment manufacturer that his very modern can washer could not deliver washed cans that would pass this test successfully with sweet-smelling low-count-bacteria cans, particularly after 50 to 100 cans had beenwashed. The accumulation of milk solid, etc., in the washing solution itself soon dissipates the dispersive and rinsing properties of any alkali cleaning solution, as discussed in a previous article ( 5 ) . Table 111-A gives the comparative data obtained from a series of consecutively alkali-washed cans, subsequently rinsed with hot water (200" F.), steam, and hot air blasts. Attention is called to the relatively high total counts which varied considerably, irrespective of the condition of the can,
although generally speaking, well-tinned cans and particularly some lacquered cans with a Lithcote surface (cans 400 and 430) tended to show better results. Most cans had high proteolytic, acid, alkali, and oxidizing bacteria counts. I n spite of the fact that most cans carried high acid-forming bacteria counts, the cans themselves were most objectionable vith their proteolytic foul odors.
Alkaline wash followed by acidified steam Table 111-B shows the results obtained when a series of consecutively alkali-washed cans were rinsed with steam charged with gluconic acid in sufficient concentration to give a pH 6.0-0.5. There is a definite improvement in all counts, as w l l as in the odor of the cans, although such improvement
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
vd. 35, NQ, 1
of vater supplies, we are apprehensive lest
supersanitation is engaged in “upsetting the balance of Kature”, We are finding that some of the influences in the quality impairment of dairy products are aclually being enhanced by the ficrupulous efforts for sanitary perfection. While we do not infer a return to “the horse and buggy days”, n-e definit’ely are of the opinion that more attention must be paid to the final freedom of cleaned equipment from films bearing spoilage types of microhea and nutrients. ~
~
~ acidrcleaner n
~
~
Table 111-@gives the coinparative data lrorn a aeries of consecut’ively washed cans
subjected t o the cleaning action of a commercial acid cleaner known as Mikro San, containing a nontoxic mixt’ure of certain organic acids, specific wetting agents, corrosion-resisting inhibiter, and microbiological depressant. Only 8 ounces of this mixture were used for charging 60 gallons Spraying Sanitary Pipes with Acid Cleaner Solution, Subsequently of water in the washing solution compartCleaned with Mofos-DrivenBristle Briish ment of the can washer. After 200 cans were washed, an additional ounce of the mixture vas added to the solution for each additional 100 cans. The cans were cleaned reniarkably is not due to germicidal action but to the release of tlie film of well and were free from n-ater spots; rubbing the finger over nutrient and bacteria as previously reported (5) the cleaned surface slioxed a definite drag which is characterAs a matter of fact, this study involving the final rinsing istic of thoroughly cleaned (not polished) metal surfaces. of cleaned milk cans with acidified steam to leave them in a After the 48-hour incubative period, the inner surfaces of the condition of acid reaction suggested the desirability of revie\\-can were dry except for the parts of t>hebottom holding 100 ing critically all equipment and utensil cleaning practice, An ml. of rinse mater. alkaline reaction obviously can lead to complications, as alAgain we note relatively lo^ total bacterial counts, with ready indicated. Then, too, there is no doubt that the more proteolytic and oxidizing types definitely inhibited; .the only spectacular and more easily controlled oxidation of dairy t y o exceptions are in cases. of very poor and rusty cansproducts and other fatty foods by nonliving catalysts has namely, 340 and 460 mhich, incidentally, compare Eavorahly eclipsed the more complex action of microbiological oxidases. with the data reported for similar cans in Table XII-A, As Jeiisen and Crettie (4) suggested, food manufacturers The collective data in the tables show the need for further and their quality control laboratories could do well t o give revision not oiilg in dairy can-washing practice but in all Lypes greater considerat’ion to the oxidative as vc.ell as hydrolytic of food sanitation and cleaning practice. Accordingly, the rancidity effects induced by microbial activity in fatty foods. possibilities of acid detergency, have been explored and, as a Relatively little attention has been paid to tlie oxidizing result, i t is soon hoped t’o develop applications in all types of capacity of microorganisnis in relation to the quality impairequipment and utensil cleaning, even including bottle washment of dairy products, We refer not only to the “cappy” ing. One marked practical effect has been the effectiveness flavor of lorv-count milks but to the surface taints in butter of acid cleaners in solving the thernioduric bacterial count and as well as tile off-flavors in cheese, all of which have becn its attendant water- and milk-stone contamination problems, incidental Lo the advancement of supersanitation in these the bane of every dairyman. industries. Castell and Garrard (1) recently reported that “the spoilage microorganisms involved demonstrate definite oxidizing properties. Organisms of the Pseudonzonns and csxPcla~sions Achromobacter genera are the most strongly oxidizing typee : Alkaline cleaning cornpounds have played s n important role those belonging to Alcaligenes and Brucella are somewhat, in many important food sanitation practices. Due to their less, although still strongly positive; members of the Aeroinherent chemical and physical properties, they have long bacter, Escherichia, and Proteus are weakly positive, variable been recognized as best adapted for such cleaning practices. or negative; the Bacilli also vary from weakly positive t o Recent experiments, lio\’i.ever, hare suggested that many negative; while the Cocci and the only Anaerobe studied of the proteolytic, alkali-forming, and oxidizing types of were definitely negative. It is also interesting to note that bacteria are favored in their quality defection of food products all organisms which mere found to be strong oxidizers villen alkaline cleaning is used. Certain conditions of hardwere Gram-negative, while those which d.efinitely Lvere n o t ness in mater supplies utilized as the solvent for many difstrong oxidizers were Gram-positive.” ferent types of alkaline cleaning compounds have been reK i t h sanitarians bending every effort in their programs to sponsible, at least in part, for the so-called milk- and watereliminate or a t least minimize natural types, such as the lactis stone deposits on dairy equipment and in cans. This disgroup normally found in fresh raw milk, and with the growing advantage presumably does not apply to acid cleaners, for realization that the strong oxidizers, such as some of the their acid character not only is corrective when used with Achromobacter and Pseudomonas types whose normal habitat water supplies predisposed to water-stone formation with is water and soil, have varying resistance to the chlorination a
c
~
January, 1943
INDUSTRIAL AND ENGINEERING CHEMISTRY
certain alkaline products but also is curative in that acids will tend to eliminate prevailing calcareous deposits, a practice now generally recognized and widely applied. It is needless to discuss the value of any cleaner that solves the milk-stone problem and its attendant difficulties with thermoduric (heat-enduring) and thermophilic (heat-loving) types of bacteria. Heretofore acid compounds have been unacceptable mainly because of their inferior detergency as well as their relatively intense corrosive action upon the metals used in food processing equipment. The discovery of organic acids with relatively low corrosiveness gave rise to the development of an acidified steam rinse in the cleaning of milk cans. The attendant inhibiting effects upon proteolytic, alkali-forming, and oxidizing types of bacteria have indicated the desirability of developing acid types of cleaners; generally, more acceptable bacterial flora survive acid cleaning practices in contradistinction to the quality-defective types apparently attendant upon alkaline cleaning. The next logical step was the development of nontoxic, relatively noncorrosive acid
105
cleaners which now are enjoying an ever-widening application in a variety of food industries. The application of wetting agents and the discovery of their effective combination with acid-reacting substances definitely indicates that the long sought acid cleaning agents, the hope and dream of many a sanitarian, are being realized. Today, therefore, acid cleaning compounds with a detergency even superior to that of most alkaline products, with the lack of any appreciable corrosiveness, and at the same time both corrective to and curative of the problem of water-stone lormation and other calcareous deposits, are indicative not only of a revision but of even greater improvement in food sanitary practices.
Literature cited (1) Castell a n d Garrard, Food Research, 5, 215 (1940). (2) Dairy I n d . Supply Assoc., Special Rept. of Tech. Comm., 1941. (3) Ellingworth, McLeod, and Gordon, J. Path. Bact., 32, 173-83 (1929). (4) Jensen a n d Grettie, Food Research, 2, 97 (1937). (5) P a r k e r , Food Industrzea, 12, No. 10,39-42 (1940).
END OF SYMPOSIUM
Solidification Point Nomograph for Fatty Acids D. S. DAVIS Michigan Alkali Company, Wyandotte, Mich.
I
N VIEW of the importance of the solidification point of
fatty acids as a criterion of purity, Hoerr, Pool, and Ralstonl presented excellent supplementary data on the effect of water in lowering the freezing points of the normal saturated fatty acids from caproic to stearic, inclusive. Their results may be correlated by the equation, w/At
=
a
+ bw
where w is percentage of water, At is freezing point depression (" C.), and a and b are characteristics of the fatty acid in question and may depend upon n, the number of carbon atoms. Data are presented conveniently and reliably (+0.02" in the line coordinate chart based upon the equation and the following constants:
c.)
No. C Atoms 6 7 8 9 10 11 12 13 14 15 16 17 18
L o q Pcr Cent Water
Fatty Acid
a
Caproic Heptylic Caprylic Nonylic Capric Undecylic Lauric Tridecylic Myristic Pentedecylic Palmitic Heptadecylic Stearic
0.394 0,383 0.373 0.351 0.370 0.479 0.467 0.574 0.551 0.651 0.743 0.820 0.912
b
Range uf u
0,289 0 . 4 - 2 . 2 1 0 , 3 5 7 0.4-2.98 0.414 0.2-3.88 0.476 0.8-3.45 0.535 0 . 9 - 3 , 1 2 0.559 0.2-2.72 0.678 0.6-2.35 0.713 0.2-2.00 0,880 0.6-1.70 0.924 0.5-1.46 1.017 0 . 4 - 1 . 2 5 1,150 0.2-1.06 1.183 0.2-0.92
F.P. of Dry Acid. C. -3.24 -6.26 16,30 12.24 30,92 28.13 43.86 41.76 54.01 52.49 62.41 60.94 69.20
The use of the chart is illustrated as follows: What is the solidification point of capric acid which contains 3.0 per cent water? Connect the point where n = 10, which represents capric acid, with 3.0 on the w scale and read the lowering of the freezing point as 1.52' C. on the At scale; then, using the table, the solidification point is 30.92 - 1.52 or 29.40' C. 1
Hoerr. C. W . . Pool, W. O., and Rslston, A. W.. Oil & S o a p . 19, 126 (1942).
