V O L U M E 23, NO. 10, O C T O B E R 1 9 5 1 Table VII.
Results Obtained for Sulfur Compounds hg Proposed Method
Per Cent Oxygen Liquid Ascarite nitrogen Compound scrubber trap Calculated Thioacetamide 4.86 0.00 None 0.06 None 8.42 Thiourea 5.79 0.05 Xone 0.02 Sone 8.92 0.06 Xone ,. 0.35 Xone 1-Methyl mercapto7.65 0.56 None ... benzothiazole Cystinea 27.10 26,92 26.65 2 6 . 6 2 26.65 26.85 27.51 27.72 Siilfanilic acid 27 72 27.96 27.31 27.72 a S a t i o n a l Bureau of Standards sample.
interferences due to extraneous liberation of iodine from the oaidant is precluded. Analysis of Samples Containing Sulfur. Although samples containing sulfur are usually converted, predominantly, to hydrogen sulfide in the reaction tube and removed by the acid gas scrubber, quantities of carbon disulfide and carbonyl sulfide are also formed which are not absorbed by the Ascarite. When these products pass through the oxidation and iodine absorption tubes, carbon dioxide and sulfur dioxide are produced n hich are subsequently retained in the micro absorption tube, giving high results for oxygen. By using a liquid nitrogen trap in place of the acid gas scrubber, the carbon disulfide and carbonyl sulfide are prevented from entering the oxidation tube. By thus eliniinating the carbon disulfide, inteifeience from that source is prevented, but because the carbonyl sulfide includes oxygen originat-
1413 ing from the sample, its removal causes low results. The data given in Table I, although not extensive, indicate that the amount of carbonyl sulfide formed is relatively small. For this reason appreciable errors as a result of the removal of carbonyl sulfide are not likely to occur when a liquid nitrogen trap is used. Table JrII shows data for several sulfur compounds, using the acid gas scrubber and liquid nitrogen trap for removing the interfering sulfur compounds. A decided advantage was indicated when a liquid nitrogen trap was employed in the analysis of these Yamples. Maylott and Lewis ( 4 ) have carried out a similar investigation on the interference of sulfui. compounds using the volunietric procedure. &Ch\OW LEDG-VENT
The authors sinceiely appiccidte the valued suggestions and advice of Harry Levin in the development of this project. Thanks are also extended to hidre\!' Ferrence, Leo F. Moore, Clayton L. Earl, and Allen Tomlins for their help in working out the details for construrting the special heating unitq. LITERATURE CITED
(1) Aluise, V. d.,Hall, R. T., Staats, F. C., and Becker, ]I-. \I-. ANAL.CHEM.,19, 347 (1947). (2) Dinerstein, R. 4.,and Klipp, R. IT.,Ibid.,21, 545 (1949). (3) Graham, J. I., and Winmill, T. F..-1.Chem. Soc. (London), 105, 1996 (1914). (4) Maylott, A. O., and Lewis, J. E., ANAL.CHEM.,22, 1051 (1950). (5) Schutse, hf., Z.a n d . Cheni., 118,245 (1939). (6) Steyermark, A., Alber, H. K., Aluise. J-. A,, Huffman, E. W.D.. Kuck, J. A,, hloran, ,J. tiitic Sat,uated inonoaliryclic Lnsarurated monoaliryclic Saturated polyalicyclic Unsaturated polyalicyclic Benzo aromatic Polybenao aromatic Fused ring aromatic 3 or 4 atom ring 5 or 6 atom ring 7 or more atom ring Other
Br, I P, As, Sb, Bi Si, Ge, Sn. P b Se, T e B , AI Other
Row
Column 33, Unsaturation
0
>c=c(
It
1
Column 37, Substitutions
I
6
-c.. 9 c-
Internal -____-
9 10 11 or more
1
Column 39
l
Internal 1 2 3 4 5 6 7 8
2 3 4 5 6 7 8
s
Wot used Solid Liquid Gas Organometallic Isotopic Indeteiminate Inorganic Polrmer 2
Column 35, Rings-Chains
1 2 3 4 5
It
Unsubstibuted Monosubstituted Disubstituted Trisubstituted Higher substituted Alpha substituted Beta substituted Gamma substituted Delta substituted
Row
o
9
10 Other
________
Part B
-1
Roa 0
1
Column 40, Carbon-Hydrogen -CHa
1 -GHa -CaH7
2
3
Column 4 2 , Oxygen
Methyl
-C(=O)OH
Ethyl
-C(=O)OR
n-Propyl
-c(=O)H
Aldehyde
\c=o
Ketone Carbonate Ortho carbonate Ortho carboxylate Alcohol, phenol
-C3H7 Isopropyl -CdHo n-Butyl 1 -GHo Isobutyl
I
LOC(=O)O-
-CdHo
sec-Butyl
C(OH)r -c(OH),
i
-CaHo
fert-Butyl
-0 H
8 9
-CaHIi 1 -GHa
n-Pentyl Phenyl
2
Y
__
_.
'
Acid. anhydride Ester, salt
__
Column 44, Nitrogen
Sitrogen-Oxygen Column 48,
Column 46, Sulfur
-
Row _ .
-C(=NH)N/ Amidine \ > X C ( = S H ) K/ Guanidine xitrilo. -=E cyano --SEX Isonitrilo -KH? n-Amine sec-Amine )SH ?1\j tert-Amine
-C (=S) S-
Thionothiolic
-C (=S) H
-SH -S-
Thioaldehyde Thione, thioketo Trithiocar. bonate Thiol Sulfide
-ss-
Polysulfide
>,-,=o
=SH
--HIS
Sulfonium
-N=N(=O)-
Azoxy
7
-0NOt
Nitrate Sitrite
8 9
'
Imine
>c=s
-sc(=s)s-
/
WC(=O)ONC(=O)N/
-C(=O)W,-< -X=C=O -0CzEPu' )N-KO~
-os0
Other Heterocyclic
\
Carbamyl Ureide, urylene Amide
0
Isocyanate Cyanate Kitro amine Nitrosoamine
3 4 5 6
1 2
X
It
V O L U M E 23, NO. 10, O C T O B E R 1951
1415
Qualitative infrared analysis involves matching the spectrogram obtained from an unknown compound with one of several thousand known standard spectrograms. The number, size, type, and location of standard spectrograms makes this operation timeconsuming. Attempts to simplify the job have resulted in many different systems which usually involve notched cards and needles. None has proved adequate and inexpensive enough to warrant general adoption. Codes and sorting s p t e m s using Hollerith cards and International Business Machine sorters have provided a new, simple, fast, accurate, inexpensive, and foolproof means of making universal searches for matching purposes. All operations can be carried out by non-technical personnel on any sorter. The cost of punching master decks of cards to index all available spectrograms is being borne by
the author's employer. Duplicate decks are available to all a t cost of reproduction. The cooperation of the American Petroleum Institute Research Project 44, the Infrared Punched Card Committee headed by E. Carroll Creitz a t the National Bureau of Standards, the American Society for Testing iMaterials, Samuel P. Sadtler, Inc., and many industrial laboratories has been assured. -4similar project for indexing the ASTiM x-ray diffraction data card file as well as author-subject search cards for infrared literature is well under way. Cards to index mass spectral data, Raman, ultraviolet, and visible absorption data as well as author-subject cards for x-ray diffraction literature and other fields, all with interlocking codes, are being considered. The savings in tinie alone resulting from the use of such cards is inestimable.
help to makc rapid, acruratc searches through data on large ~iumbers of cards to locate one or a fen pertinent spectrograms which may tir removed directly from the file and turned over to competent infrared workers for final analysi9 The savings in time,
details of absorptions, chemical structure, physical proprxrties, and a reference to the location of the original data o r spectrogram for a given compound, but only the latter reference is printrd on the card. The cards enable more or less nontechnical
Table I. Row
Column 4 1
0
1
,
1 2
Column 4 3 , Oxvaen -H20
_
Oxonium
*
_
_
--N=N--X/
nx=s ES
Part H (Continued)
Column 45, h-it rogen _
\
+
~-:
,\
/
~
~
-
.
-so2
Triazine Diazonium Quaternary animoniiini hnimonium
Nitro h-itroso Isonitroso, oxime Aniino oxide
--s-0
-s=o
'\
>so
Column 49. Nitrogen-Oxygen
i _Colunin _ _ 4~ ~_ -
-
Cyanamide
I
1 Row -, 0 1 2
l 3 I 4 5 6 7 8
l : Column, 50 Nitrogen-Sulfur
Row
Ti1
-___
Column 52. Ox) gen-Sulfur
- --
1
Column 54, Sitrogen-Oxygen-Suliur
'
>NC(=S)N
SC(=S)S-
Thiocarbamrl
-OC(=S)O-OC(=O)S-
Thiocarbonate
\XC(=S)O/KC(=O)S-
2
1
-C(=S)N-
, X SS/"
>ss
Sulfilimine
-0so-
2~ 5 A
Sulfenate
Other Heterocyclic
Coluinn 51
1 2 l
d) ccyanate y~l thio~ ~
F
Column 53, Oxygen-Sulfur
I
---I-
0
CI
I 1
Acyl isothiocyanate Sulfamide
nr,
P
As, Sb Si
\q-y-
0
\/SS(O?)S(
~
1
Y
Row -
-_____
Diarnino sulfide
9
Row
=
l
B
Sulfime. etc. Suliamino
6Heterocyclic L
Sulfinate
(
-1
Isothioc yano
-X=S
Y
-~(=0)0-
Thiocyano
8
X
-_
Column 56. Other Elements
--S(SOaK)z Other Heterocyclic
Other Heterocyclic
Column 55, Nitrogen-Oxygen-Sulfur
Column 57. Inorganic Esters
1
Row
I-
i
>so,
Sulfate
-S(OdX
