Jul), 1931

1 1 - D U S T R I A I, A N D

E N G I N E E I 1 I N G C I E M I S T R Y
(1928).

743

of e-braw and of a-brav may not be analogous in all details). It ii reaqonable to assume, however, that in regard to the two general mechanisms of corrosion leading to either a residual or a redeposited corrosion product, the -brass and a-brash are analogous.

(4) Bradley and Thewlis, Proc. Roy. Sac. (London), -4112, 678
(5) Graf, .IletalZrcirtschaft,11, 77 (1932)). (6) Nixon, Trans. Electrochem. Soc., 45, 297 (1924). (7) Rhodes and Carty, IND. ENG.CHEW, 17, 909 (1925). ( 8 ) Stillwell and Stout, J . Snz. C'hcm. Soc., 54, 2593 (193'2). (9) Storey, M e t . R. Chem. Eng.. 17, 653 (1917). (10) Thum, Ihid., 26, 301 (1922).
RFEEIVED hlarch 19, 1934. Presented before the Division of Physical a n d
Inorganic Chemistry a t t h e 86th hieeting of the .imerican Chemical Society, Chicago, Ill., September 10 t o 15, 1933

LITERATURE CITED
(1) Abrams, Trans. Electlochem. Soc , 42,39 (19221 (2) Bassett, M e t & Chem Eng , 27, 340 (1922). (3) Beutel and Kutalnigg. Z l1etaZZhnde 21, 412 (1929).

Effect, of Aging upon Oils in Chrome Leather'

EDWIN R. THEIS . ~ N DJ. 31. GRAHAM, Lehigh University, Bethlehem, Pa.
30 per cent. This a m o u n t of effect of hydrogenAging of chrome-tanned leather affects the oil insoluble in petroleum ether concentration upon ratio of free and combined oils in the leather. d o e s n o t c h e c k w i t h the inadsorption and the As leafher ages, some of the absorbed oils, effect of various oils upon oil creased amount of oil removed especially the sulfonated or polar groups, comadqorption a n d resulting by s u c h s o l v e n t s as alcohol, bine with the leather and cannot be extracted. acetone, and chloroform. When strength of the finished leather the oils are of a low sulfonation, have already been shown ( 4 ) . Comparisons of these effects are made f o r mixI n the previous wcirk the shaved the petroleum ether appears to tures of sulfonated neat's-foot, castor, and cod c h r o m e - t a n n e d leather was r e m o v e a l m o s t a l l of t h e oils. A s leather ages, the free oil hydrolyzes soluble or free oil. The writers treated with a particular type and becomes rancid, and this effect progresses of fat liquor a t a given temperabelieve, in view of all the conthroughout a n aging period. W i t h most oils flicting evidence, that the values ture, and the leather was washed, of free oil obtained by petrodried, and analyzed for oil by aging reaches a n equilibrium within 2 weeks the official American L e a t h e r leum ether extraction are more af ter f a t-liquor ing. C h e m i s t s ;Issociation method nearly the c o r r e c t values. In Such e#ects as noted here hat!e a practical which u s e s petroleum ether as v i e w of t h e fact that the fatbearing upon leather which needs to be degreased; solvent. M a n y years ago liquored leather is dried before if the leather is degreased shortly after fatWilson ( S )criticized this method e x t r a c t i o n , they believe that of e x t r a c t i n g leather and admost of the s u l f o n a t e d o i l liquoriny, more free oil will be remoted by the v i s e d the use of chloroform as fraction is removed from the naphtha than after aging 2 weeks, and such the solvent removing the greatl e a t h e r . On the other hand, effects will necessarily hare their effect upon the est quantity of oil. He pointed they think that acetone, alcohol, Jinished leather. Data show that degreasing out that petroleum ether as used or chloroform tends to dissolve remoues only the free oil in the leather, and the w o u l d n o t r e m o v e from the some of the oil actually bound leather such oils as m o e l l o n s in the skin and with the chrofeel and temper of the resulting leather must and sulfonated oils, and showed mium compounds. In the case be due to the oil actually combined with the that chloroform would extract of c o m p o u n d s s u c h a s t h e leather. these oils. Stiasny and Riess moellons, continuous extraction (2) have pointed o u t t h a t in a liqui'd-liquid extractor a fraction bf the sulfonated oils is insoluble in petroleum extracts them more or less completeiy.' For- these reasons ether but soluble i n , acetone and alcohol. Stather and the writers believe that petroleum ether extraction represents Lauffmann (1) in their work on the fat-liquoring of chromed more nearly the free oil content of the leather. However, hide powder used petroleum ether and alcohol. They if chrome-tanned leather is fat-liquored with a mixture found that even the drastic extraction with alcohol did of raw and sulfonated oil and another sample fat-liquored not remore all of the adsorbed oil and termed this residue with the same total concentration of raw oil and sufficient ('bound'' fat. soap for emulsification purposes, the petroleum ether will Although it is true that petroleum ether will not extract all extract more oil from the leather fat-liquored with raw of the sulfonated oil from the leather, i t extracts a great por- oil than from the sample fat-liquored with sulfonated oil. tion of it. In the analysis of many sulfonated oils by the This result may possibly be explained by the fact that the Schindler method modified by Theis and Graham (S), i t was sulfonated or polar fraction of the sulfonated oil actually found that the petroleum ether extracted from alcohol solu- combines with the leather. This combination may be of tions of various sulfonated oils varying quantities of the three distinct types: (a) combination with the skin itself, treated oil. The amounts of oil remaining behind after ( b ) entrance of the sulfonated or polar fraction of the sulcontinuouq extraction with petroleum ether varied from 9.1 to fonated oil into the chromium complex, and (c) formation of 50.5 per cent. Table I shows results as obtained by the actual chromium soap. modified Schindler method for various sulfonated oils. This investigation mas undertaken in order to determine However, for many of the sulfonated oils actually used in the the changes in the fat content of chrome-tanned leather fat-liquoring of chrome-tanned leather, the polar or sulfonated during aging. It had been noticed in some previous work fraction (insoluble in petroleum ether) varies between 10 and that, as leather aged, the petroleum ether extractive became less as time of aging increased, and the writers wished to find 1 This paper IS the third of a series o n "Fat-Llquorlng of Chrome Leather" out if combination with the leather took place a t the time of (4)

744

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 26, No. 7

fat-liquoring or whether such combination took place over an extended period of time.

oil mixtures; three samples of sulfonated and raw cod oils, the same strength as that used in the neat's-foot oil mixtures. After fat-liquoring, the excess liquor was squeezed out through and the fat-liquored hide powder allowed to dry TABLE I. ANALYSES BY MODIFIED METHOD ON VARIOUS TYPES cheesecloth, at room temperature OF OILS overnight. The (Per cent of moisture-free oil) following day, FREE UNsamples of each lot FATTY NH~UTRAL SAPONIPOLAR were extracted in a SAMPLE ACID OILS FIABLE 1 2 3 Total So x h 1e t apparatus 8.63 20.4 ... 29.0 Sulfonated cod oil 1 22.3 27.8 ... w i t h low-boiling Sulfonated neat's-foot 7.1 ... 9.4 p e t r o l e u m e t h e r . ... 2.3 31.3 oil 1 75.2 12.5 ... 50.5 ... 19.2 15.3 27.0 Sulfonated castor oil 1 ... 1.3 33.5 ... 34.8 A f t e r complete ex18.4 37.7 Sulfonated olive oil ... 8.6 33.2 ... 41.8 traction, the residues 18.3 33.1 Sulfonated corn oil 51.4 ... 12.8 16.2 ... 29.0 were digested with Sulfonated cottonseed oil 10.8 6.14 15.3 ... 21.4 constant-boiling hy63.7 Commercial fat liquor 2 14.9 0:82 10.1 . . 10.1 Commercjal fat llquor 3 80.8 3.6 55.4 14.4 16.8 .. T&e 16.8 drochloric acid for 5.0 Commercial fat liauor 4 Sulfonated nsat'slfoot hours , the oil 2 39.0 27.1 ... 27.5 ... 27.5 several acid hydrolysate was Sulfonated castor oil 2 37.8 17.7 . . . 4.6 3i:3 . . . 36.9 Sulfonated cod oil 2 33.1 54.0 ... 4.79 2.0 17.0 ... 19.0 p l a c e d in a l a r g e Commercial fat liquor 1 24.8 6.2 40.5 15.9 Trace 20.7 s e p a r a t o r y funnel and shaken out with carbon tetrachloride. EXPERIMENTAL PROCEDURE ' Fat Licuors: Raw T h e c a r b o n tetraSulfonated Neatsfoot Oil Neatsfoot Oil Standard hide powder was pickled, chrome-tanned (using 6 chloride removes the I I I I I per cent Tanolin R), and neutralized. Representative samples u n o x i d i z e d f a t t y 0 rc 4 6 a of the chromed hide powder were then fat-liquored with con- matter. After this Weeks a f t e r fat-lic.uoring treatment t h e acid FIGURE VARIATIONOF FREE FATTY m i x t u r e s t i l l con- ACIDS IN2.EXTRACTED FATFROM AGED tained oxidized fatty LEATHER FOR MIXTURES OF SULFONATED FREE OIL acids; it was there- AND RAW I1 NEAT'S-FOOT OIL WTH TIME fore filtered and the 25% S u l f . oxidized fatty matter was dissolved in warm alcohol. In this way the petroleum ether 50% Sulf. removed the free oil, while the hydrolysis freed the combined oil and allowed it t o be extracted with the carbon tetrachloride and alcohol. Subsequent samples of the hide powder were extracted 1, 2, 4, 8, and 12 weeks after fat-liquoring. The 75% S u l f . data obtained from these experiments are shown in Tables 11, 111, and IV and in Figures 1 t o 5.

Fat Liquors:

Sulfonated ljeatsfoot Oil Raw Neatsfoot Oil

DISCUSSION OF RESULTS
The data for the mixtures of sulfonated and raw neat's-foot oil show that during the first week after fat-liquoring an increase in the combined unoxidized fat occurs and becomes more pronounced as the amount of sulfonated oil increases in the original fat-liquoring mixture. In the case of the 75 per cent sulfonated oil mixture, this increase in combined oil extends well over into the second week of aging. After the second week of aging there is no further evidence of an oil change within the leather. Further, the free oil (extracted by petroleum ether) decreases rapidly during the first week of aging and thereafter shows little or no change. After the second week little change is noted in the fat content itself, but another change is taking place as is shown in Figure 2. Hydrolysis of the free fat itself is taking place, resulting in free fatty acids. This hydrolysis appears to occur throughout the entire aging period. The percentage of free fatty acids in the free oil amounts to nearly 50 per cent in the case of the higher sulfonated oil mixture. It would seem that the constituent in the fat liquor combining with the leather is the sulfonated oil; otherwise there would be some agreement between the formation of free fatty acids and the combination of the oil with the leather. I n the case of the sulfonated and raw castor oil mixture, the results obtained are somewhat different. As in previous work, there is a decided decrease in free oil and a decided

4 6 8 Weeks a f t e r Fat-Liquoring

FIGURE 1. VARIATION OF FREE AND COMBINED FATFOR MIXTURES OF SULFONATED AND RAW NEAT'S-FOOT OIL WITH TIME

stant shakin a t 120" F. for one hour with 20 per cent of the fat liquor; t%is percentage was based on the wet weight of the hide powder. Nine different fat liquors were used and consisted of: three mixtures of sulfonated neat's-foot oil and raw 15" F. cold test neat's-foot oil, containing 25, 50, and 75 per cent of the sulfonated oil, respectively; three mixtures of sulfonated and raw castor oil of the same strength as that of the neat's-foot TABLE11.
Sulfonated oil:
V.4RI.4TION

O F FREE AND COMBINED FATIK FAT-LIQUORED CHROME HIDEPOWDER WITH TIME A F T E R FAT LIQUORING FOR MIXTURES OF SULFONATED AND RAWNEAT'S-FOOT OIL

VARIATION IN F R ~ I FAT O 25% 50% 75%

36.6 32.7 33.5 33.6 33.1 31.5
33.1 28.7 29.5 29.5 29.2
28.0

7 days

1 day

15 days 4 weeks 8 weeks 12 weeks

38.3 33.6 34.0 34.1 33.5 31.8

VARIATIONIN COMBINED FAT Total punoxidized 25% 50% 75% 25% 50% % of dry fat-liquored hide powder 2.22 4.30 6.79 2.73 4.69 2.86 5.55 8.45 3.32 5.77 2.91 5.83 8.80 3.27 6.32 2.87 5.71 8.67 3.40 6.24 2.70 5.32 8.42 3.05 5.82 2.87 6.50 8.76 3.24 5.92

75%

COMPN. OF FREE FATTY ACIDS 25% 50% 75%

%
7.23 8.88 9.28 9.00 8.85 9.07 7.8 14.0 21.5 25.7 38.3 45.3

%
15.1 18.2 23.3 29.6 41.0 48.2

%
24.6 25.0 29.4 31.9 45.9 50.5

July, 1934

INDUSTRIAL AND ENGINEERING CHEMISTRY

145

40 depending a great deal upon the increase in combined oil during type of oils used in the fat liquor. the first week of aging, but in Extractives Cried at 105C. f o r 5 h o u r s k These processes might be listed : this case it extends well into the ( a ) combination of the sulfoFat Li3uors: S u l f o n a t e d Castor Oil second week for the 25 per cent Raw Castor Oil nated or polar groups with the sulfonated oil mixture, and into hide fiber, (b) entrance of the sul2 the third week for the 50 and 75 fonated or polar groups into the per cent mixtures. I n addition $ sol chromium nucleus, (c) processes there is a second period during 2 c h a r a c t e r i s t i c of oil tannage which the combined oil increases. following combination in some With the 75 per cent mixture the 2 cases, and (d) hydrolysis of the second period continues on from g free oil into high percentage of the first period and i s q u i t e % free fatty acids, which do not noticeably due to oil oxidation. 2 FO contribute to the combination After 8 w e e k s t h e r e is a n ineffect as far as can be noticed. crease in the unoxidized portion Conditions a and b are espeof the combined oil for the 75 cially noticeable in the higher perand 50 per cent sulfonated oil centages of sulfonated oils. ConE mixtures. It is quite possible G. dition c is specially noted for that in this case we have an oil castor and cod oils, which would t a n n a g e due to the h y d r o x y loo 10 12 more or less be expected. group of the ricinoleic acid of the Beeks after Fat-Liquoring The hydrolysis of t h e f r e e castor oils. With this set of exFIGURE 3. VARIATION OF FREEFAT FOR MIXTURES oil into free f a t t y a c i d s unperiments, as in the case of the neats-foot oil mixtures. hvOF SULFONATED AND RAWCASTOR OIL WITH TIME doubtedly comes about through , i n t e r a c t i o n of t h e o i l itself drolysis of the free oil proceeds a t with the acid contained within the leather. As the leather almost constant rate as shown in Table 111. The sulfonated and raw cod oils used as the fat liquors give ages, the extracted free oil shows a progressively increased the results shown in Figure 5. In the samples fat-liquored acid value. If, as has been postulated, petroleum ether will not extract with the 25 per cent oil mixture, there is no change in the unoxidized combined oil but there is an increase in the oxi- sulfonated oils, how is i t possible to explain the decrease in dized oil during the first 4 weeks. With 50 per cent sulfo- what we call free oil during the aging of the leather? Is i t nated oil there is a slight increase in the unoxidized oil and a possible that the absorbed sulfonated oils become more decided increase in the oxidized combined oil, especially insoluble as the leather ages? The writers do not believe this to be the case. It would more naturally follow that the during the first 2 weeks of aging. I n the case of the 75 per cent mixture there is an increase in the unoxidized combined reason for the decrease in free oil and the increase in combined oil during the f i s t week. During the second week there is an oil is due to the sulfonated or polar groups actually combining with the skin fiber or entering the chromium complex in such increase in the oxidized combined oil. Considering the experiments as a whole, it would appear a manner as to resist extraction. The petroleum ether that, during aging, several distinct processes are at work,

40

1
Extractives Cried at 105C.for
5 hours

1h. I
/ A
%--#

Total Combined Fat Unoxidized Combined Fat

OI n

c)

I.J-

Total Combined Fat Unoxidized Combined Fat

//

P
E59
I

*-+

Sulf.

----a-

--______ &-------__
I I

------

Weeks after Fat-Liquoring

FIGURE 4. VARIATION OF COMBINED FATFOR MIXTURES OF SULPONATED AND RAWCASTOR OIL WITH TIME

746

I X D IJ 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 ST R Y
VARIATION O F

Vol. 26, No. 7 TIME 4 F T E R FAT

OF

TABLE 111.

FREEAND COXBINED FATIN FAT-LIQUORED CHROME HIDE POWDER LIQUORING FOR MIXTURES OF SULFONATED AND RAW CASTOR OIL
FREE FAT
75%
25.8 21.1 20.1 19.2 15.3 10.8
V.4RIATIOh' IX C O M B I N E D

WITH

vARI.4TION I N

Sulfonated oil: 1 day 7 days 15 days 4 weeks 8 weeks 12 weeks

25%
38.0 32.4 32.3 30.0 27.4 25.6

50% 32.9 27.8 27.3 25.6 24.1 20.0

-Unoxidized7 25% 50% 75% % of d r y fat-liquored hide p o w d e r 3.45 7.39 11.80 4.90 9.73 14.81 5.26 10.32 16.08 5.43 10.72 16.65 5.49 10.2 17.0 5.96 13.7 20.8

FAT

7 -

25%
3.87 5.41 5.71 6.04 5.83 6.35

Total 50%
7.84 10.20 11.00 11.43 11.3 14.4

75%

Comw
25%

FREE FATTY ACIDS

50% 75%

%
17.35 19.5 22.3
12.40 15.47 16.60

%
13.6 17.9 19.5 24.5 31.5 39.1

%
24.6 23.3 25.2 30.2 38.9 46.0

7.5 11.7 15.7 20.2 29.4 35.0

TABLE Iv*.

VARI.4TIOK O F

FREE AND

COMBINED FATI N FAT-LIQUORED CHROME HIDE POWDER WITH LIQFORING FOR MIXTURES OF SULFON~TED AND R a w CODOIL

TIME AFTER F ~ T

VaRI4TION I N

Sulfonated oil

25%
7

FREE FAT 50% 75%

29.6 27.8 25.5 23.1 24.5 22.8

1 day 7 days 15 days 4 weeks 8 weeks 12 weeks

36.7 34.4 34.3

30.5

31.0 29.9

34.0 31.8 28.8 27.1 26.6 26.6

?5% 50% 75% % of d r y fat-laquored hide p o u d e r 2.21 4.16 6.68 2.14 4.80 7.88

-7

-VARIATION Unovidized

8.01 7.92 7.77 8.11

IN

COWBINED F ~ T
25%
2.93 3.69 4.62

Total50% 5.40 6.34

C O W N OF FREE FATTY ACIDS

75%
8.12 9.22 11.32 11.4 11.70 11.49 25% 50%

75%

%
8.01 8.20 8.27
8.14

%
15.2
22.2 28.6

%
26.0 28.0 32.0 3i.1 38.4 41.5

2.31 2.48

2.26 2.63

4.20 4.83 4.60 4.95

5.09

4.80 4.55

8.6 21.2 21.7 24.5 25.9 30.6

31.5
32.1 37.2

extractive is usually very light or "oily" colored and seldom ever has the greenish cast of chromium compounds, whereas a chloroform extractive will in many cases show a greenish color indicative of the extraction of chromium compounds of one type or another. It is true that, if the chloroform extractives are analyzed for chromium, it will be found to be very small; but, if the polar groups should enter the chromium complex, the percentage of chromium would necessarily be small and the fatty acids large, especially if the complex is olated in character. In view of their work, the writers believe that petroleum ether extracts most of the oil that exists really free in the leather and that chloroform extracts not only free oil but oils actually in combination with any free

chromium salts in the leather and with the chromium combined with the hide fiber.
LITER.4TURE C I T E D

(1) Stather and Lauffmann, Collegium, 1932,391, 672, 940. (2) Stiasny and Riess, Ihid., 1925, 498; J . I n t e r n . SOC.Leather Trades Chem., 10, 150 (1926); J. Am. Leather Chem. Assoc., 21, 76 (1926). (3) Theis and Graham, Ibid., 28, 52 (1933). CHEW, 23,50 (1931); 24,799 (1932). (4) Theis and Hunt, ISD.ENG. (5) Wilson and AMerrill, ".lnalysis of Leather," McGraw-Hill Book Co., N. Y., 1931.
RECEIVED April 16, 1934. Presented before the Division of Leather and Gelatin Chemistry a t t h e 86th Meeting of the American Chemical Society, Chicago, Ill., September 10 to 15, 1933.

Relation of Volume Change to the Mechanism of Rubber Vulcanization

IRAWILLIAMS, E. I. du Pont de Nemours & Company, Wilmington, Del.
M O S G the many partial e x p l a n a t i o n s of t h e mechanism of vulcanization, several require a polymerizing action at some step in t h e p r o c e s s ( I , 7 , 11, 14, 16, 17). The actual mechanism of the polymerization is u s u a l l y not and in c e r t a i n cases it is p r o b a b l e that the

term t~PolymeriZationli may be i n t e n d e d " t o cover some type of phenomena not involving primary valence forces. A concept of the mechanism of vulcanization involving polymerization is more or less logical follon-ing the discovery of the polymerization of butadienes to rubber-like bodies. The polymerization of isoprene which causes a loss of half of the double bonds produces a more or less plastic body, and a further polymerization to an increased molecular weight could conceivably cause the loss of plastic properties which results in rulcanization. This mechanism has been suggested for the vulcanization of plastic chloroprene polymer ( 3 ) , although little evidence exists t o support such a process.

Rubber-sulfur mixtures increase in density during in direct proportion to the amount of sulfur combined. No change in denSifY has been found Which would indicate either an increase or decrease in the number of double bonds during culcanization. The reaersion point of rubber during tulcanization, at least in certain cases, corresponds to the time of practical disappearance of accelerator.

The existing evidence points almost entirely to the absence of polymerization d u r i n g vulcanization. Spence a n d Scott (12 ) have p r e s e n t e d evidence based on iodine absorption to show that no decrease in unsaturation Occurs which be directly a c c o u n t e d for by of sulfur. Fisher and Gray ( 6 ) have s t u d i e d by the s a m e m e t h o d rubber vulcanized with nitro bodies or benzoyl peroxide. The authors conclude that any change in unsaturation was less than one per cent. The ability of rubber to combine with 32 per cent of sulfur without the evolution of more than small quantities of hydrogen sulfide is a further indication that little disappearance of unsaturation has taken place because of polymerization. It should be possible to determine the extent of polymerization by following the change in density. During the polymerization of isoprene the specific gravity changes from 0.68 to approximately 0.90, or by a value of 0.22 with a loss of