tivity of the oximes and the resolution available in this region, one should be able to determine very small amounts of oximes in a wide variety of samples. Alcohols which absorb a t 2.74 t o 2.76 microns should not interfere, and oximes and alcohols could probably be determined in mixtures. Phenols absorb in the same region as oximes and with roughly equivalent intensity ( I ) , so that in most cases they might be expected t o interfere 11-ith the determination of oximes. Hydroperoxides, which absorb at 2.81 to 2.84 microns, would not be expected to interfere ( 1 ) . illthough we have no data to prove the point, it should be possible to determine oximes in the presence of most cther nitrogencontaining compounds, including amines and amides, because their fundamental NH bands are observed a t 2.8 to 3.0 microns ( 5 ) . Oximes should be determinable with both good sensitivity and selectivitj b y
LITERATURE CITED
Table 1. Near-Infrared Data on Oximes at 2.78 Microns Molar Absorptivity Liter/MoleCm. 2-5 0 . 1 4 . 3
Oxime5 p mM m M Cyclohexanone 2.776 183 222 2-Butanone 2.i76 1i2 206 n-Butyraldehyde 2 779 188 205 Acetophenone 2 783 200 244 Benzaldehyde 2 i85 238 254 All samples Distillation Industries, Eastman grade, used as received. b Rave length corrected as described (3).
c Measured on Beckman DK-2 spectrophotometer, operating conditions as described (5).
the use of near-infrared in the 2.78micron region.
(1) Barnard,
D., Hargrave, K. R., Higgins, G. hl. C., J. Chem. SOC.1956,
2845.
(2) Goddu, R. F., ANAL. CHEY.29, 1770 (1957). (3) Ibid., in press. (4) Goddu, R. F., Delker, D. A,, Ibid., in press. (5) Jones, R. N., Sandorfy, C., ‘Chemical
Applications of Spectroscopy,” W. West, ed., pp. 510-13, Interscience, New York, 1956.
Analytical Division Hercules Powder Co., Inc. Research Center Wilmington 99, Del.
ROBERTF. GODDU
RECEIVEDfor review June 13, 1958 Accepted July 30, 1958. Portion of a paper presented a t the Pittsburgh Conference on Analytical Chemistry and Applied Spectroscopy, March 1958.
174.
Potassium Hexachloro-osmate, K20sC16, and Potassium Hexabromo-osmate, K20SBr6 A. G. TURNER, Jr., A.
F. CLIFFORD,
and C. N. RAMACHANDRA RAO
Richard B. Wetherill Laboratory of Chemistry, Purdue University, Lafayette, Ind.
CCULLOUGH ( 2 ) studied the crystal structures of potassium hexachloro-osmate and potassium hexabromo-osmate and found that they crystallize in the cubic lattice, possessing the ammonium chloroplatinate structure (3) with an 0; symmetry. The intensities reported by ;\IcCullough were only visual estimates and he did not give the powder diffraction data for the chloro compound. The authors have now investigated the crystallography of these compounds using a Geiger-counter x-ray diffractometer with Cu K a radiation. The samples were prepared by the procedure of the National Bureau of Standards (4). Potassium hexachloro-osmate was prepared b y the method of Gilchrist (1). One gram of osmium tetroxide (Goldsmith Bros., Chicago) was dissolved in 2.5 ml. of water and 10 ml. of concentrated hydrochloric acid. Five milliliters of ethyl alcohol was then added and the mixture refluxed for 4 hours. The solution was sloa-ly evaporated on a steam cone to a thick, brown sirup. Potassium chloride solution (15% .by weight) was added and the solution was evaporated again and cooled in a n 1708
ANALYTICAL CHEMISTRY
ice-water bath. The precipitated potassium hexachloro-osmate was filtered by suction, washed thoroughly with alcohol, and dried in air. The product thus obtained was recrystallized several times from 10% hydrochloric acid solution, dried a t 98” C., and stored in a desiccator. CRYSTALLOGRAPHY Crystal System. Cubic. Space Group. OR. Cell Edge. 9.82 + 0.02 A. Density. 2.03 (x-ray). Refractive Index (5893 A.) 1.825 =k 0.005. Potassium hexabromo-osmate was prepared by a procedure analogous to that used for the hexachloro-osmate, with care that the temperature did not rise too high during the evaporation steps (less than 50’ C.). CRYSTALLOGRAPHY Crystal System. Cubic. Space Group. OF;. Cell Edge. 10.37 =t0.02 A. Density. 2.68 (x-ray). DISCUSSION
It is clear from the diffraction data that potassium hexachloro-osmate and
X-Ray Diffraction Data hkl
K20sC1~ I d
111 200 220 311
5.680 4.928 3.466 2.962
440 531 442 600 533 622 444 711,551 640 642 553,731
1.734 1.658 1.634
~
... ...
1.417 1.376 1.359 1.312 1.278
100 33 28 23 11 18 20 11 9 11 15 6 4
... , ,
,
4 6 5 6 4
K20sBr6 d I 100 6.021 5.226 3.693 3.1‘75 2.991 2.586 2.373 2.315 2.116 1.993 1.835 1.754 1.729 1.579 1.562 1.497 1.452 1.439 1.383 1.348
61 9 29 82 62 9 22 7 17 35 9 9 4 4 31 4 2 1 4
hexabronio-osmate are isomorphous as expected, the spacing of the latter compound being uniformly about 6% greater. The lattice constants reported here differ from those of AIcCullough (W), who
+
+
LITERATURE CITED
compounds were examined under a microscope and found to crystallize as small, \\.ell defined octahedra (K20sC16) and rhombic dodecahedra (K20sBr,).
found 9.729 0.02 z and 10.30 0.03 A for K20sC16 and K20sBr6, respectively. The lattice constant of the former compound corresponds rather closely t o the value reported by the Sational Bureau of Staiidards for (SHJ2PtCl6 ( 3 ) . The authors' intensity determinations differ considerably from the visual estimates of 1\IcCullough (2) and seem to follow m acceptablc ordrr of variation with the planes of r d w t i o i i . In addition, both
(1) Gilchrist, R., Bur. StandardsJ * Research 9, 282 (1932). ( 2 ) ,1fcCullough, J. D., Z. Krist. 94, 143 (1936). (3) Swanson, H. E., Gilfrich, N. T., Ugrinic, G. hl., S a t l . Bur. Standards, Circ. 539 (1955). (4) Swanson, H. E., Tatge, E., Ibid., 539 (1953). CRYSTALLOGRAPHIC data for publication in this section should be sent to W. C. 1tcCrone. 500 East 33rd St.. Chicago 16,
ACKNOWLEDGMENT
The authors express their thanks to
H. J. yearian, Department of Purdue t-niversity, for the use of his laboratory facilities.
Ill.
Analysis of 2-Bromoethanol, 1.2-Dibromoethane, 1,1,2,2-Tetrabromoethane, and i -Bromo-2-(2-bromoethoxy)-Ethane Mixtures cs-57
1. R. KILEY, The Dow Chemical Co., Midland, Mich.
Instrument: Perkin-Elmer M o d e l 12, NoCl prism Sample Phase: Solution in carbon disulfide No.1
AA or Lengfh Av 1 mm
Name
1 2-Bromo-
1
0-20
C?H:BrO
~
zt0.3
2.8p 2.7 2.9
10.5
8.44y
ethanol
-I
-1-
2
1,2-Dibromoethane
CnHdBrz
0-50
Cell Windows: NaCl Absorbance Meosurement:
0.090 100 0 . 0 4 9 ~ 0.1
Calculofion:
___ -I 0.300 100 0.071p1 0 . 1
Relative Absorbancera-Anolyticol
1
1 Bromo-2-(?-bromoethoxylethane
C,HaBriO
1,1,2,2-Tetrabromoethane
CsH2Brr
0-50
2.8
1 2
0.945 0.000 0.000 0.000
!
8 . 9 2 ~ 0.350 0 . 0 7 7 ~ 0.1
3 4
Point-X-
Successive approx.-Mofrix:
8.44 0.234 0.648 0.194 0.015
8.92 0.187 0.013 0.916 0.037
14.25
0.058 0.003 0.002 0.446
I
I
- -~ ~ _ _ 4
1 f0.3
Inverse m a t r i x - X GraphicolL-
ComponentlX
-.
3
Base l i n e - L
_ _ _ I_ _ _ _ _ _ 1 4 . 2 5 ~ 11.400 1 100 0 . 2 4 5 ~ 0.1 I
Materiol Purify:
Reference compounds 99 +% pure
Relative absorbances are given as the slope o f the Beer's l a w concentration curves used expressed in terms of obsorbance p e r 100% o f constituent.
Analysis of 2,4-Dichlorophenoxyacetic Acid 1.
R. KILEY,
The Dow Chemical Co., Midland, Mich.
CS-58 ~ - _ _ _ ~ - - _ _ _ _ _
I
~- l
Component Name Formula
I
No.
.
1 2,4-Dichloro-
ICsH,ClrOs
%%d
I
2 2,6-Dichloro-
1'
1
1
I
phenoxyacetic ocid
%
1
AC~U-
racy
%
1
X or
1
B.L. Pts.
1
Slit
Concn.
(mm) 1 mg/ml
1 AA or
1
Av
1 Length
1
mm
150-1001 f1.0 113.85pl1.000 1 100 10.174pl 0.1
1
_______
1
l
Range
I
k
l__l__l___ 13.58
~
1
0.800
~1
'~0.140p
100 0.1
Instrument: Perkin-Elmer Model 12, N a C l prism Sample Phase: Solution in acetone Cell Windows: N a C l Absorbance Measurement: Calculation:
~
~
1 I
chlorophenoxyocetic acid
-_______-
1
10*094p'
I
These d a t a represent standard piibliration and submission is open t o anyone in accordanre with regulations of ..\SAI,STICAL CHEMISTRY.T h e Coblentz Society is acting only as a n aid t o t h e journal.
~
Relotive Absorbancesa-Analyticol ComponenflA
_ _ _ I_ _ _ 1 f0.5 1 3 . O O p ~ o . 8 O o 1 ~ 2 phenoxy, 10.139pl 0.1 3 l acetic acid 4 -~ ~ -___ _ _ _ l1- _ -1-1 4 Di-(2,4-diCi4H&lrOll 0-20 1 0 . 5 9.39p0.450 100 Moterial Purity:
-
Base line-
Inverse m a t r i x - X Graphical---
13.85 0.426 0.084 0.168 0.165
Point
2-
Successive approx.---
' Matrix:
~
13.58
13.00
0.148 0.254 0.122 0.145
0.149 0.212 0.888
0.208
9.39 0.235 0.213 0.215 1.240
Reference compounds 99 +% pure
Relative absorbances a r e given as the slope o f the Beer's law concentration curves used expressed in terms o f absorbance p e r 10070 of constituent.
T o standardize procedures, ASILYTICALCHEMISTRY requests t h a t material be sent in quintuplicate t o t h e chairman of t h e review committee: Robert C . Wilkerson, Celanese Corp.. of America. Post Office Box 8, Clarkson, Tex.
VOL. 30, NO. 10, OCTOBER 1958
1709
