T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
514
of insoluble phosphoric acid, since i t thought a method which would give more concordant results was needed. Since there are several factors which influence the determination of insoluble, such as the neutrality of the ammonium citrate, time required for filtering insoluble, etc., the best way of attacking the problem seemed t o be to vary one of the factors a t a time, keeping the others constant. The first question taken up was the preparation of neutral ammonium citrate. A solution of citrate was prepared by one of the members of the Committee and sent out with the samples. Those to whom samples were sent were asked t o prepare a citrate solution and run samples with the solution prepared by them and also with that sent out by the Committee. The results' showed that i t was possible to prepare a solution which would give results which were the same as those obtained by the Committee citrate, but results from different analysts showed great variation between them. One of the chief causes of this great variation was due to the great difference in time required for filtration. Another set of samples was prepared and together with these samples was sent a standard sample on which the Committee had determined the total phosphoric acid. The total in standard sample ran about the same as the highest insoluble. The instructions which accompanied were the same a s those sent out with the previous lot of samples, except t h a t t h e method of filtration was shortened by transferring the precipitate t o another filter in cases where filtration was difficult. The results2 showed some improvement in the case of goods difficult t o filter, b u t in the case of acid phosphate the variation between analysts was the same. The results obtained on the last set of samples are somewhat disappointing. The differences d.0 not follow any rule, hence it is difficult t o assign any reason for the variation. The most probable cause of the variations is due t o the failure, on the part of the analyst, to observe the details of the method closely. Analysts who have had considerable experience with the method think that much better results should be obtained where the details of the method are closely observed. [ J . Q. BURTON
V O ~6. , S O .6
The determinations as reported herewith were made on three samples which were prepared and averaged with the greatest care by hlr. G. H. Savage and t h e formulas used by him are given below in detail in as much as it has a direct bearing on the present report. The various ingredients which went to make up these three compounds were weighed with extreme accuracy and compounded with the greatest care in order that uniform average samples might be obtained. The vulcanized compounds were then ground according t o the requirements of the procedure under investigation, carefully mixed and placed in small vials which held the approximate amount required for the various determinations. These were sent by express to the various members and the analysis on the first determination started by each member within approximately twenty-four hours of the time of grinding the sample. These samples were re-analyzed a t intervals as indicated in the report. This Committee respectfully refers the members of the Rub6 , 75, for the complete method of ber Section t o THISJOURNAL, procedure of the Joint Rubber Insulation Committee as followed by this Committee in the analysis of the three samples prepared by Mr. Savage. The formulas of the three compounds, together with the analytical results obtained, are tabulated below. FORMULAS USED
IN
PREPARING COMPOUNDS ANALYZED B 309
A Fine P a r a . . . . . . . . . . . . . . . . . . . . 297 Hard Paraffin,. . . . . . . . . . . . . . . 25 Ceresine.. . . . . . . . . . . . . . . . . . . . . . . 19 Sulfur., Litharge 70 Zinc Oxide.. 350 Whiting ...................... 239 ~~
...................... ..................... .................
C 324
..
.. ..
25 19
19 70 350 237
70 350 227
-
__
1000
~
1000
1000
No corrections, additions or omissions have been made in reporting these analytical results. The analysts' numbers refer W. Boughton; a-D. W. Whipple; t o the following: I-E. 3-W. A. Ducca; 4-G. H. Savage; 5-J. B. Tuttle. SAMPLE A-FIRST
ANALYSIS
......
[ G. FARNHAM, Chairman =PORT
OF THE ANALYTICAL COMMITTEE-RUBBER SECTION AMERICAN CHEMICAL SOCIETY
,[The following report was presented t o the Rubber Section of the A. C. S.a t Cincinnati on April 8, 1914,and the Section authorized its publication for t h e purpose of bringing the results obtained t o the attention of those interested in the work and in answer t o the Joint Rubber Insulation Committee's request for criticisms. DORRISWHIPPLE,Secretary. I Your Committee begs to present herewith the third report of t h e investigations made by this Committee, together with the results obtained. The major part of the work of this Committee has been confined to certain methods of procedure as outlined by the Joint Rubber Insulation Committee for the analysis of materials used for insulating purposes. The results obtained on preyious work were presented t o the members of the Rubber Section at the Milwaukee meeting and at the Rochester meeting. The Committee has not included the previous work in the present report (although the same has a direct bearing on the present report) as some of the methods have been changed or revised. I n the time intervening between the Rochester meeting and the present day, this Committee has investigated the completed preliminary procedure of the Joint Rubber Insulation Committee and these final results are the ones tabulated below. 1 THIS JOURNAL, 3 (1911). 118. 3
I b i d . . 6 (1913). 956.
Analyst's No. 1 1 2 2 3 4 4 5 D a t e of Extraction with Acetone 11/13 11/15 11/14 11/20 11/20 11/13 11/13 11/13 T o t a l Acetone Ext r a c t ( % ) . . . . . . . . 4 . 1 6 4.12 3.97 4 . 0 3 4 . 1 8 3 . 8 4 3 . 7 8 4 . 0 8 Free Sulfur (%). .... 0 . 8 7 0 . 8 6 0.80 0 . 8 2 0 . 9 0 0 . 7 0 0 . 6 6 0.82 Unsaponifiable M a terial (70) ........ 2 . 9 7 2.70 2 . 7 6 3.29 2.71 2.69 2.69 Waxy Hydrocarbon A ( % ) . . . . . . . . . . . 2.29 2 . 2 5 2 . 1 8 2.27 2.39 2.31 2.40 Waxy Hydrocarbon B ( % ) . . . . . . . . . . . 0 3 4 0 . 2 0 0.32 . . 0.56 0.14 0.20 0 . 1 1 Total Waxy Hydrocarbon ( % ) . . . . . . 2 . 6 3 2.45 2 . 5 0 . . 2.83 2.53 2.51 2.54 B y Difference Organic Extract (yo) 3 . 2 9 3 . 2 6 3.17 3 . 2 1 3 . 2 8 3 . 1 4 3 . 1 2 3 . 2 6 Saponifiable Acetone 0 . 4 3 0 . 4 3 0.57 E x t r a c t (%) . . . . . . 0 . 3 2 0 . 5 6 0 . 4 1 Unsaponifiable Res0.18 0 . 1 8 .. ins ( 7 0 ) . . . . . . . 0 . 3 4 0 . 2 5 0 . 2 6
......
..
..
. . . .
. . . .
SAMPLE A-SECOND ANALYSIS AnaIyst'sNo ........ 1 D a t e of Extraction with Acetone... . . . 11/20 T o t a l Acetone Extract(70). . . . . . . . 4.13 0.88 Free Sulfur (%) Unsaponifiable M a terial(%) . . . . . . . . 2.32 Waxy Hydrocarbon A (7") . . . . . . . . . . . 1.97 Waxy' -Hydrocarbon B ( % ) . . . . . . . . . . . 0.17 T o t a l Waxy Hydrocarbon ( 7 0 ) . . . . .2. . 5 5 B y Difference Organic Extract (%) 3 . 2 5 Saponifiable Acetone Extract (yo) ...... 0 . 9 3 Unsaponifiable Resins (%).. . . . . . . . . 0 . 1 8 Fillers (%) Sulfurfree
.....
................
1
2
2
3
4
4
5
11/21 11/25 11/23
12/4
11/20 11/20 11/20
4.16 0.79
4.14 0.88
4.02 0.80
3.72 0.89
3.90 4 . 0 0 0.65, 0.65
2.75
2.82
2.81
2.54
2.41
2.51
2.60
2.31
2.31
2.37
2.32
2.11
2.32
2.51
4.20 0.91
0.24
0.25
0.19
0.49
0.10
0.10
0.11
2.64
2.56
2.56
2.81
2.21
2.42
2.62
3.37
3.26
3.22
2.83
3.25
3.35
3.29
0.62
0.44
0.41
0.29 0.84
0.84
0.69
0.20
0.26
70.7
..
0.25 71.6(a)
.. ..
72168 73.75
( a ) T h i s determination was not made b y the same analyst.
0.09
..
..
71. I
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-
