(2) Bjerrum, J., Acta Chens. Scand. 9, 1407 (1955). (3) Ewing, G. W., “Instrumental Methods of Chemical Analysis,” pp. 311-13, McGraw-Hill, New York, 1954. (4)Hallett, L. T., Graham, R. P., Furman, N. H., Diehl, H. C., Ashley, S. E. Q., Churchill, H. V., ANAL. CHEU. 24, 1348 (1952).
( 5 ) Jordan, J., hlleman, T. G., Zhid., 29,
9 (1957). (6) Jordan, J., Ben-Yair, hl. P., Abstracts of Papers, XIIth International Congress of Pure and Applied Chemistry, pp. 42-3, Xew York, N. Y., September 1951. (7) Jordan, J., Ben-Yair, M. P., Brkiv Kemi 11, 239 (1957).
(8) Keily, H. J., Hume, D. K.,ANAL. CHESI. 28, 1294 (1956). (9) Linde, H. W.,Rogers, L. B., Hume, D. N.,Zbid., 2 5 , 404 (1953). (10) Willard. H. H.. Merritt. L. L.. ’ Dean, J. i., “Instrimental kfethods or Analysis,” pp. 594-8, Van Nostrand, Princeton, 1958. (11) Zenchelsky, S. T., Periale, J., Cobb, J. c., A N A L . CHEM. 28, 67 (1957).
176. ,Copper Etioporphyrin II PETER K. IBER, The Johns Hopkins University, Baltimore, Md.
C
OPPER etioporphyrin
I1 (C32H36N4C~) containing the reflections (h01), (Okl),
was synthesized and crystals were grown in dimethyl formamide. They are very soft needles, about 5 mm. long and 0.5 mm. thick. They are opaque, violet in reflected light; the smallest crystals (0.1 mm. thick) are clear and red in transmitted light. The material decomposes in the solid state a t approximately 350’ C. The crystal structure of the related compound nickel etioporphyrin I has been described (1). Precession photographs (CuK, radiation) n’ere taken of the reciprocal nets
and ( h l l ) . They show the crystals to be monoclinic, with the following cell dimensions: a = 14.23, b = 20.31, c = 4.76 A. (all &0.3%), p = 90’0’. The space group PZ1/n is uniquely determined by the systematic omissions (h01 observed only with h 1 even and OkO only with k even), which also confirm the holohedral point group 2/m, indicated b y the morphological development. Tlyinning on (101) is fairly common; occasionally three crystals occur in one t x i n related as follows: I to I1 by
Table 1. hkl
110 020 120 200 210 220 040
Za
&obsd.b
8 8
0,00759 0,01006 0.01504 0.02017 0.02274 0 02932 0 03916
5 5
5 4 4
0.04753 0.05963
+
Powder Data for Copper Etioporphyrin II
&o.led.’
0.00736 0.00968 0.01462 0.01976 0 02218 0 02944 0 03872 0.04688 0.04663 0.05883
0.14607 0.16783
{ {0.05848
0.17539
:1
0 06599
0.06643 330 221 131)
0.07167 0.08228
(0.00624 0.07365 0.07093 0.08026 0.08318
{
(0.08867
0.24528
350 260)
O ’‘0407
E:)
0 11089
25 1 0,12606 510
E\ 450J
3
0.08787 0,10471 0.10269 /0.1041)6 10,10688 0.10965 0.11045 (0.12447
{
i::;;:$! 0.12592 0.13627 0.13954
0.14917 0.14503 0,14528 0.16773 0.16616 0.17684 0.17464 0.17579 0,17739 0.17784 0.18652 0.18420
0.30184
0.31518 0.31959
1
262 3 10 0 391. 571 70 1 ill,
0.20643 (0,22821 0 22447 0 22372 0 24228 0.24549 0.24734 30 24335 0.24308 0 24383 0 24463 (0.26396 10.26031
I I
0.26496 0.26399 (0.28661
0 10 1‘
0,28372
3
0.28610
0.30036 i[0.30271 0.30276
{
0.31635 0.31877 0.32144 0,32212
0.32739
0.18949 , O . 18752 0.20725
410 060 141)
reflection in (101), and I to I11 by reflection in (ioi), where I1 and I11 have parallel orientations. A crystal Iyas measured on the twocircle goniometer ( 2 ) . The quality of the signals was fair in the prism zone and poor in (101). The best averaged value for m:m’ = (110):(170) is 74’24’, which gives a:b = 0.7054 (morph.), as coinpared to 0.7006 (x-rays). The angle plol, between the c axis and the normal t o (101), is 16’28’, which gives a n approximate ralue c:a = 0.2956 (morph.), as compared to 0.3345 (x-rays). This
0.28686 0.28501 0.28629 0.28642 .O ,28884
0.34088
1.10,2’ 133 930 223. 722 2.13.0 4.12.0,
2
0.42649
I\
;
0.32933 0.32603 0.34245 0.34300 0.34063 0.36565
I
0.36298 0.42418 0,42461 0.42216 0,42733 0.42873 0.42942 0.42810 0.44155 0.44477
0.44083 0.44590 Z. Relative intensities estimated visually on a scale of 8. b &,,bed. = 4 sin28/k2 = l/daObsd. c Qcald. = l/d2(hki) = h ’ ~ * ~ k2h*’ Pc*2 2lhc*a* cos @*. 5
+
VOL. 30, NO. 12, DECEMBER 1958
+
+
2065
X-RAYDIFFRACTION DATA
leads to c:b = (a/b)(c,‘a) = 0.2085 (morph.) against 0.2344 (x-rays). The discrepancy in the density determinations is ascribed to inaccuracy in the obserx ed density, due to the small size of the available crystal (1.7 mg.). A pori-der pattern (Table I) was taken in a Philips camera with the sample mounted in a thin-walled capillary tube.
elle Donnay, Geophysical Laboratory, and to J. D. H. Donnay, The Johns Hopkins University, for guidance in both theory and practice of crystallography.
Space Group. P21/n. Cell Dimensions. a = 14.23 A., b = 20.31 A,, c = 4.76 A. (all 10.3%). Formula Weights per Cell. 4. Formula Weight. 540.21. Density. 1.21 f 0.08 grams per cc. (Berman balance); 1.305 1 0.013 grams per cc. (x-ray).
LITERATURE CITED
(1) Crute, hf. B., dissertation on “Crystal Structure of Sickel Etioporphyrin 11,” The Johns Hopkins University, Baltimore, Md., 1958. (2) Smith, Esther, Corwin, A. H., “Use of the Goniometer in the Identification of Organic Compounds,” Abstracts of Papers, 97th Meeting, American Chemical Society, Baltimore, Md., April 1939, p. 52M.
ACKNOWLEDGMENT
CRYSTAL MORPHOLOGY Crystal system. Monoclinic. Form and habit. Keedles elongated parallel to c. Shovving rhombic prism { 1101, pinacoids { O l O ) and { 101). Twinning fairly common (see above). Axial Ratio. a:b:c = 0.7054:l: 0.2085 (based on morphology): 0.7006: 1:0.2344 (based on x-rays), Beta Angle. 90’0’.
This research was supported in part by a grant from the Petroleum Research Fund administered by the American Chemical Society. Grateful acknowledgment is hereby made to the donors of said fund. The copper etioporphyrin was supplied by A. H. Corwin. Sincere thanks are also due to Gabri-
%
Determination of trans Unsaturation (Expressed as Elaidic Acid) in Fatty Acids
CRYSTdLLOGRAPHIC data for publication in this section should be sent to IT. C. McCrone, 501 East 32nd St., Chicago 16, Ill.
Determination of Carbon Monoxide and Carbon Dioxide in Air CSM-65
R. 1. SCHEDDEL, The D o w Chemical Co., Midland, Mich.
J. E. CALLEN a n d 2. T. PACE,
CS-63
The Procter and Gamble Co., Cincinnati, O h i o
Slit
I No
1
Component Name Formula
_
_
Eloidic I Cl,Hi,O?
I
i _
1 Range
5
_
_
X B.I.
Accurccy
-
-
0-100 10.6
_ I
I Concn. Slit
~
(mm)
1
Points
_
AA ~ ~
-
10.36
I 10.13-
,
1
g/l length mm
_
_
0.250 1 20 0.051~ 0.5
No.
-
10.67
I
1
,
.
Carbon monoxide
~
co
~
%
I
_
mm
AA or Av
length cm
_______
_
700
0.209
0-40 I_____-l___
1
1
c0S~Di-l 10.05
Carbon dioxide
~
I
I
4 . 2 6 ~ 0.186 700 3.8- 0.033~ 5 5.2 ~
Instrument: Boird Associates M o d e l A, NaCl prism Sample Phase: Gas, 700 mm. Hg pressure Cell Windows: NaCl Absorbance Measurement:
Base line
Calculation:
Culculation: Graphical Relative Absorbance-Analytical Matrix:
Bose l i n e - X
Inverse matrixGraphicalX
Point-
Successive approx.-
Relative Absorbances~-Analytical M a trix: Component/h 4.62
10.36~ 0.460 I./g.cm.
4.26 0.745 0.000 0.000 7.820 Reference compounds 99 $% pure
1
2 Material Purity:
Reference compounds 99 $% pure
Material Purity:
Range
Concn.
(mm)
I
2
Instrument: Perkin-Elmer Model 12-C, NaCl prism Sample Phase: Solution in carbon disulfide Cell Windows: NaCl Absorbance Measurement:
-
-.
Component Nume Formula
a Relative absorbances are given as the slope of the Beer’s law conof centration curves used expressed in terms of absorbance per constituent.
Determination of trans Unsaturation (Expressed as Methyl Elaidate) in Methyl Esters J. E. CALLEN and 2 . T. PACE, The Procter a n d Gamble Co., Cincinnati, O h i o
No.
Component Name Formula
’
Range
Accuracy
CS-64
X
Slit
B.L.
(mm)
Concn. g/l Length
AX
mm
9
1
Instrument: Perkin-Elmer M o d e l 12-C, NaCl prism Sample Phase: Solution in carbon disulfide Cell Windows: NaCl Absorbance Measurement: Calculation:
Base line
Graphical
Relative Absorbance-Analytical Matrix:
~~
elaidate
,
0.250 20 0.051~ 0.5 10.59
These d a t a represent standard publication a n d submission is open t o anyone in accordance with regulations, of AXALYTICAL CHEMIBTRY.T h e Coblentz Society is acting only as an aid t o t h e journal.
2066
e
ANALYTICAL CHEMISTRY
Component/X
1
10.36~ 0.416 I./g.cm.
~
Material Purity:
Reference compounds 99 +%pure
T o standardize procedures. AN.ALYTICAL CHEMISTRY requests t h a t material be sent in quintuplicate t o t h e chairman of t h e r e n e w commlttee: Robert Wilkerson, Celanese Corp. of America, Post Office Box 8, Clarkwood, Tex.
c.
