June, 1914
T H E J O r R Y A L OF I N D C S T R I A L A N D ESGI,VEERING C H E M I S T R Y SAMPLE A-THIRD
1 Analvst's S o . . .... D a t e of Extraction with Acetone.. . . . 1214 T o t a l Acetone Extract (%). . . . . . . . 4.08 Free Sulfur.. . . . . . . . 0 . 8 2 Unsaponifiable M a terial ( y o ). .. . . . . . 2 . 8 1 Waxy Hydrocarbon -4 (YC).. . . . . . . . . . 2.30 W a x y Hydrocarbon B (yo). . . . . . . . . . . 0.34 T o t a l Waxy Hydrocarbon ( % ) . . . . . . 2 . 6 4 B y Difference Organic E x t r a c t (%) 3 . 2 6 Saponifiable Acetone Extract ( % I . . . . . 0.45 Unsaponifiable Resins (%) . . . . . . . . . . 0.17
2
12/5
12/9
12/12
4.06 0.87
3.97 0.80
3.97 0.83
2.77
2.84
1
.. ..
4.08 0.72
4.01 0.75
4.28 0.96
2.73
..
2.78
2.80
2.68
.. .. .. .. .. ..
2.30
2.30 0.14
2.53
2.47
2.44
3.19
3.17
3.14
0.42
0.33
0.41
0.24
0.37
0.29
ANALYSIS 2 3
11/13 11/15
11/14 11/20
4 04 0.73
3.95 0.80
3.92 0.75
3.85 0.67
2,54
2.59
2.82
2.67
1.94
2.05
2.08
2.09
0.29
0.27
0.36
0.17
2.42
2.41
2.43
0.11
0.16
0.11
2.53
2.57
2.54
3.36
3.26
3.32
0.58
0.46
0.64
0.25
0.23
..
4
4
Analyst's No. . . . . . . . D a t e of Extraction with Acetone . . . . . T o t a l Acetone Extract(70). . . . . . . . F r e e s u l f u r (570) . . . . . Unsaponifiable M a terial(%) . . . . . . . . Waxy Hydrocarbon A (Yo
5 12/4
0.17
2
4 12/'4
2.25
1
4 12/4
0.28
SAMPLE B-FIRST
Analyst's h'o.. . . . . . . D a t e of Extraction with Acetone.. . . . T o t a l Acetone E x t r a c t (70). ....... Free Sulfur ( y o )... . . Lnsaponifiable M a terial (7c) ........ W a x y Hydrocarbon A (ro)... . . . . . . . . \Vaxy Hydrocarbon B (yo). . . . . . . . . . . T o t a l Waxy Hydrocarbon (7'3). . . . . . By Difference Organic E x t r a c t (yo) Sapunifiable Acetone E x t r a c t (Yo),. . . . . Unsaponifiable Resins (R). . . . . . . . . .
ANALYSIS 2 3
1
2.23
2.32
2.44
2.26
3.31
3.15
3.17
3.18
0.77
0.56
0.35
0.51
._
0.52
0.54
0.83
0 31
0.27
0.38
0.41
._
0.28
0.20
..
3.73 0.56
4.24 0.86
2.65
2.63
2.55
2.15
2.18
2.23
0.22
0.25
2.37
2.43
.. ..
3.li
3.17
3.38
....
.......
Analvst's X o . . D a t e of Extraction
terial (70) . . . . . . . . W a x y Hydrocarbon A (70)... . . . . . . . . W a x y Hydrocarbon
B
(Yo) . . . . . . . . . . .
T o t a l W a x y Hydrocarbo? (70), ,.,, . B y Difference O r g a n i c E x t r a c t (%) Sanonifiable Acetone Extract (70).. . . . . Unsaponifiable Resins ( y o )... . . . . . . .
SAMPLE B-THIRD 1 1 2
ANALYSIS 2 3
4
5
11/20 11/20 3.95 0.69
4.23 0.85
2.56
2.58
2.09
2.39
0.16
..
2.25
..
3.26
3.38
0.70
0.80
0.31 72.85 6913
4
4
5
12/4
1215
12/9 12/12
12/4
12/4
12/4
12/4
4.03 0.88
3.95 0.i8
3.86 0.73
3.75 0.57
4 00 0 92
3.98 0.71
4.12 0.79
2.il
2.78
2.72
2.61
2.36
2.69
2.61
2.57
2.26
2.08
2.10
2.10
2.18
2.31
2.22
2.32
0.21
0.47
0.28
0.22
0.54
0.11
0.18
..
2.47
2.53
2.38
2.32
2.72
2.42
2.40
..
3.94 0.75
3,15
3.17
3.13
3.19
3.18
3.08
3.27
3.33
0.44
0.39
0.41
0.58
0.82
0.39
0.66
0.76
0.24
0.25
0.34
0.29
..
0.27
0.21
.,
SAMPLE
Analyst's KO. . . . . . . . 1 D a t e of Extraction with A c e t o n e . . . . . I I / 13 T o t a l Acetone E x tract (%). . . . . . . . 1.55 Free Sulfur (YC) ., . . 0 . 7 9 Unsaponifiable M a terial ( % ) . . . . . . . . 0 . 2 5 Waxy Hydrocarbon A (Yc) . . . . . . . . . . . .. W a x y Hydrocarbon B (%) . . . . . . . . . . . 0 . 0 9 T o t a l W a x y Hydrocarbon (70). ..... B y Difference Organic E x t r a c t (%) 0 . 7 6 Saponifiable Acetone E x t r a c t ( 7 0 ) .. . . . . 0 . 5 1 Unsaponifiable Resins (70) . . . . . . . . . . 0 16
..
C-FIRST 1 2
ANALYSIS 2 3
4
4
5
11/15 11/14 11/20 11/20 11/13 11/13 11/14 1.44 0.76
1.48 0.74
1.40 0.70
0.22
0.18
0.26
. . . . . .
1.72 0.89
1 , l 5 1.09 0.52 0.55
1.58 0.85
0.60
0 51
0.17
0.63
0.44
. . . . . .
0.05 0.06 .. 0 . 1 8 0 . 1 1 .. . . . . . . . . . . . . . .
0.05
0.68
0.74
0.70
0.83
0 63
0.54
0.73
0.46
0.56
0.44
0.23
0.12
0.10
0.56
0.17
0.13
0.20
0.33
0.33
..
..
1.52 0.81
1.58 0.77
1.47 0.76
1.47 0.74
0.26
0.27
0.15
0.18
0.06
SAMPLE B-S ;ECOXD ANALYSIS
2 2 3 4 1 1 Analyst's No . . . . . . . . D a t e of Extraction with Acetone.. . . . 11/20 11/21 11/24 11/25 11/20 11/20 T o t a l Acetone E x . . . . . . . 4 . 0 4 4 . 0 4 4 . 0 1 3 . 9 2 4.30 4 00 t r a c t (7c). 0 . 8 0 0.81 0 . 7 7 0 . 7 3 0 . 9 7 0 73 Free Sulfur ( y o ) . Unsaponifiable M a . . . . . . . 2 . 5 4 2.52 2.74 2 70 2 . 7 3 2 11 terial (70). n ' a a y Hydrocarbon A (70). . . . . . . . . . . 2 . 0 2 1 . 9 5 2.24 2 . 2 8 2 . 2 0 1 91 TTaxy Hydrocarbon B (yo). . . . . . . . . . . 0 . 2 3 0 . 3 4 0 . 2 0 0 . 2 6 0 . 6 4 0 14 T o t a l W a x y Hydrocarbon ( % ) . . . . . . 2.25 2.29 2.44 2 . 5 2 2 8 4 2 05 By Difference Organic E x t r a c t (%) 3 . 2 4 3 . 2 3 3 . 2 4 3 . 1 9 3 . 3 3 3 27 Saponifiable Acetone . Extract (%). . . . . . 0 . 7 0 0 . i l 0 . 5 0 0 . 4 9 0 . 6 0 Unsaponifiable Res.. ins ( % ) . . . . . . . . . . 0 . 2 9 0 . 2 3 0 . 3 0 0 . 1 8 . _ 6 7 . 8 71.6(a) . . . . 74:SO Fillers (%I,. . . . . . . . (a)This determination was not made b y t h e same analyst.
.. ..
11/20 11/21 11/25 12/4
carbon ( y o ) . . 0.06 B y Difference O r g a n i c E x t r a c t ( % ) 0.71 Saponifiable Acetone Extract ( % ) . . . . . . 0 . 4 5 Unsaponifiable Resins ( % ) . . . . . . . . . . 0 . 2 0 Fillers (%) . . . . . . . . . 7 1 . 8 ( a ) This determination was
11/13 11/13 11/14 3.70 0.53
SAMPLE C-SECOND ANALYSIS 1 1 2 2 3
4
4
5
11/20 11/20 11/20
..
1.39 0.67
1 . 4 0 1.74 0.69 0.83
..
0.10
0.11
0.17
. . . . . . . . . . . . . . . . . .
5
.. .. _. _. .. .. ..
515
.
.4nalvst's X o . . . . . . . . D a t e of Extraction with Acetone.. , . . T o t a l Acetone Ext r a c t ( 7 0 ) .. , . . , , , Free Sulfur (%) . . . . . Unsaponifiable M a terial (Yo). . . . . . . . Waxy Hydrocarbon A (YC). . . . . . . Waxy Hydrocarbon ........... B (W) T o t a l Waxy Hydrocarbon ( y C ), ,, , , , B y Difference Organic E x t r a c t ( X ) Saponifiable Acetone Extract(%) . . . . . . L-nsaponifiable Resins (yo). . . . . . . . . .
0.05
0.05
0.05
0.05
..
0.73
0.72
0.71
0.91
0.55
..
0.62
0.60
0.74
0.05
0.05
0.06
0.05
0.05
0.81
0.71
0.54
0.56
0 . 2 1 70.10 . . . . . . ,1.4(a) . . . . 74:i not made b y t h e same analyst.
SAMPLE C-THIRD 1 1 2
..
.. .. ..
0.06
ANALYSIS 2 3
4
75:43 7 0 : ?
4
5
12,'4
12/5
12/9
12, 12
12:4
1214
12/4
12/4
1.49 0.80
1 .44
0.79
1.34 0.70
1.47 0.76
1.19 0.79
1.44 0.6i
1.42 0.67
1.62 0.82
0.22
0.28
0.25
0.20
0.23
0.35
0.31
0.15
0.29
'
0.06
0.06
0.05
0.08
..
. . . . . . 0 07 0 . 0 5 ..
0.06
0.06
0.05
0.08
..
0.07
0.05
, ,
0.69
0.65
0.64
0.71
0.40
0.77
0.75
0.80
0.47
0.37
0.39
0.51
0.17
042
0.44
0.65
0.16
0.22
0.17
0.12
..
0.28
0.26
..
. . . . . . . . . . . .
At a meeting of the Analytical Committee held in ITashington on March 20, 1914, the undersigned members of the Committee unanimously agreed to report to the Rubber Section and to those interested in the work, the following recommendations : I-The results of our investigations have shown that the determinations of acetone extrgct, free sulfur, total waxy hydrocarbons and total sulfur are sufficiently accurate and reliable to warrant our endorsement. a-The results of our investigations have shown that the determination of fillers is inaccurate and unreliable and therefore the calculation of the amount of rubber as prescribed by this procedure is equally inaccurate and unreliable. 3-The results of our investigations have shown that the contributing steps for the division of resins into saponifiable and unsaponifiable resins are inaccurate and unreliable; therefore, the sum of the two should be reported as resins present and no division of resins indicated. E. Vi'. BOUGHTON J. B. TUTTLE W. A. DUCCA P. H. WALKER G. H. SAVAGE D. 1%'. WHIPPLE,Chairman COMMENTS OF JOINT RUBBER INSULATION COMMITTEE ON REPORT O F ANALYTICAL COMMITTEE OF RUBBER SECTION OF T H E AMERICAN CHEMICAL SOCIETY, APRIL 8 , 1914 The Joint Rubber Insulation Committee desired criticisms of its preliminary report that inaccuracies may be corrected before the final report is issued, and wishes to thank the Analytical Committee for the work it has undertaken in this connection. The publication of the results of the Analytical Committee has been authorized by the Rubber Section. In spite of this, a close examination of these results shows their value to bedoubtful. The Analytical Committee has drawn conclusions from results of this and its previous reports and has endorsed four of the determinations, namely, the acetone extract, free sulfur, waxy hydrocarbons and total sulfur. The chloroform extract and the alcoholic potash extract have not been criticized. The report draws two other conclusions from the data pub-
T H E J O U R N A L O F I N D r S T R I A L A X D EL\TGIAVEERILVGC H E M I S T R Y
516
lished, one of which concerns the determination of fillers and the other, the division of resins into saponifiable and unsaponifiable. There has been but one compound analyzed, of which there are three variations: one with paraffin, one with ceresin and one without waxy hydrocarbons. We understand t h a t these were made from the same lot of raw rubber. They contain practically the same percentages of the various mineral ingredients, so t h a t the determinations of fillers and of resins are practically a repetition of the determinations of one compound. The Analytical Committee draws general conclusions as to the value of these determinations from the results on this one compound. No data are given on the raw rubber and we cannot judge whether i t contained the normal amount of insoluble matter. From the tables of the Analytical Committee i t appears that all the results on fillers are too high. It is possible t h a t the compound used may have certain characteristics which magnify t h e errors of the determination. It is known t o the Committee that errors may occur and the subject is being investigated. It has been the experience of the Committee that the magnitude of these errors is less after practice with the procedure. We have assumed above that all members of the Analytical Committee followed the prescribed procedure absolutely. An examination of the results on the different constituents of the acetone extract indicates t h a t the procedure has not been followed by all the members of the Analytical Committee. I n this connection we would like to call attention to the following note in the tentative report of this Committee (THIS JOURNAL, 6 , S I ) : “With a procedure of this length, it is impossible t o explain every detail without undue elaboration and the Committee wishes to point out t h a t while to experienced chemists the procedure may seem overburdened by detail, yet every specified detail was found necessary in order that the conditions essential t o accurate and consistent work might be reproduced by all chemists using the procedure. For this reason it is extremely important t h a t all lnstructions be observed even if their significance is not perceived by the individual chemist. It will probably be found that even with the instructions properly observed, some experience will be needed to apply the method successfully. ’ ’ The results given for Compound A ( I I / Z O and 1 1 / 2 1 ) under No. I on Total Waxy Hydrocarbons, contain what may be assumed t o be a clerical error. However, in all the results given under No. 3 we can find no clerical error t o account for the absurdity of the results. For instance, in every case but one there is a greater value given for total waxy hydrocarbons than for unsaponifiable material, which, according t o the procedure, is a n absolute impossibility. We do not attempt to explain the results, but we do point out that the results are necessarily in ,error and cannot be considered in judging the procedure. The results under S o . 4 for total acetone extract and free sulfur are consistently.low. If the results under A-os. I, 2 and 5 are averaged and compared with the average results obtained by No. 4, it wiIl be seen that the lower results on free sulfur probably account for the lower acetone extract of KO.4. Act. Sample A Ext. Av. Nos. 1 , 2 and 5 , . . . . . . 4 . 0 7 Av. No. 4 . . , . , , , , . , , , , , , 3 . 8 1
Free
S
0.83 0.68
Act. Ext. 4.13 3.95
Free S 0.85 0.65
Act. Ext. 4.0i 4.05
- -0 . 1 _ _ 0 . 2_ 0 0.02 5 0.18
Difference . . . . . , . . , . , , , . , 0 . 2 6 Sample B Av. Nos. 1, 2 and 5 ..... , . 4 . 0 0 A v . N o . 4. . . _ . . . . . . . . . . .3 . 7 2
.
0.55
4.05 3.98
0.79 0.71
0.21
0.07
0 . 0 8 -0.01
0.77
1.56
0.78
0.76
3.98 3.99
- - _ _ _ - -
Difference . . . . .. , , ... . . . . 0 . 2 8 Sample C Av. Nos. I , 2 and 5 ....., , 1 . 4 9 Av. No. 4 . . .. .. , , , . , , , , , 1.12
.
Difference
..... . . . . . . . . ,
,
1.40 0.68 - - 0 . 5-4 _ - -
0.37 0.23 0.16 (a)Very poor checks
0.10
Free S 0.86 0.74 0.12 0.79
0.82(a)
-0.03
1.47 1.43
0.77 0.67
0.04
0.10
These results indicate t h a t the acetone extraction was not properly made. The Committee believes that the prescribed form of extraction apparatus was not used, and that used would
Yol. 6 , No. 6
account for the loss of free sulfur and the consequent lower acetone extract. Another apparent discrepancy in the results can be explained on close examination. If we average all the results on saponifiable acetone extract, obtained by Nos. I , 2, 4 and 5, on each variation of the compound analyzed, we obtain the following: AVERAGESAPONIFIABLG ACETOKE EXTRACT Analvst’s No. 1 2 4 5 Sample A . . . . . . . . . . . . . . 0 . 5 5 0.40 0.60 0.63 Sample B . . . . . . . . . . . . . . . 0 . 6 0 0.48 0.66 0 . i9 Sample C . . . . . . . . . . . . . . . 0 . 4 7 0.50 0.52(a) 0.65 ( a ) Eliminating results of 0.10 and 0.12, 11/13, obviously in error
.
The averages given under No. 2, on Samples A and B are lower than those obtained by Nos. I , 4 and 5, and on examination of the acetone extracts obtained by hTo. 2 , it will be seen that he obtained consistently lower results than Nos. I , 2 and 5. The results indicate that the acetone extraction was not properly made and t h a t this has probably caused lower saponifiable resins. If we, therefore, eliminate the results of No. 2 , those obtained by Nos. I, 4 and j for “A” and “B” are about what we would expect from this compound. \\‘hen we come to results for “C,” we do not see how any conclusions can be drawn. The object of the separation of the resins into saponifiable and unsaponifiable was t o differentiate between different rubbers, and we are sorry that the Analytical Committee did not investigate other rubbers in order t o show the differences between them. Considering the results as a whole we are of the opinion that the report of the Analytical Committee would have had more bearing on the procedure under consideration if that procedure had been carefully followed. We hope that the work of the Analytical Committee will lead to other criticisms in order that we may avail ourselves of the experience gained this year, and incorporate whatever improvements we may decide upon in a later report. JOINT RUBBER INSULATIOX COMMITTEE WM. A. DEL MAR,Secretary April 29, 1914
-
AMERICAN INSTITUTE OF CHEMICAL ENGINEERS
6th SEMI-ANNUAL MEETING, TROY,JUNE
17-20,
I914
PROGRAM OF PAPERS 1 . Address of Welcome. HOXORABLE C . F. BURSS,Mayor of Troy. 2. Presidential Address. hl. C. WHITAKER. 3. The Saratoga Septic Tanks (Lantern). WM. P. MASON. 4. The Application of Physical Chemistry t o Industrial Processes. W. F. RITTXAS. 5 . Studies o n Filtration. J . W. BAINand A. E. WIGLE. 6 . Scrubber for Vacuum Apparatus for Laboratories. CHARLES BASKERVILLB. 7 . Shoddy a n d Carbonized Waste. L. J. MATOS. 8. A Combination Water Softener and Storage Tank (Lantern). L. M. BOOTH. 9. The Present P a t e n t Situation. M. TOCH. IO. Ozone and Ventilation. J. C. OLSENA N D Wzf. H. ULRICH. 1 1 . Bleaching Cotton Fiber. J. C . HEDDEK. 12. Development of Rotary Furnaces (Lantern). R . K. MEADE. 13. A n Oil Shale f r o m Nevada (Illustrated). CHARLES BASKERVILLE.
EXCCRSIONS Laboratories of Rensselaer Polytechnic Institute. U. S. Arsenal (Heavy Guns). Geo. P. Ide & Co. (Collars and Shirts). General Electric Co. Plant a t Schenectady. Saratoga (The N. Y .State Reservation, the Springs and Sewage Disposal Plant). Water Works a t Albany (Slow Sand Filter Beds and Mechanical Scrubbing Filtersj. West Virginia Pulp & Paper Co. Plant a t Mechanicsville. Burden Iron Works (Puddling Process for Wrought Iron). Cohoes Filter Plant (Mechanical Filters). Freihoffer Baking Co.
