mined by calculatingffrom the observed x-ray intensities and hv referrine to Figire 3. The most imnortant contribution to the experimental error in f arises from the lack of reproducibility of scattering intensities recorded by the diffractometer. Optimum precision can be obtained by the use of slow scanning speed, and by averaging several values , the ratio contains two of I ~ / l n where intensity values from the same run. It was found from 18 determinations that the standard error in f due to lack of instrument reproducibility is about 2%; the inclusion of other experimental errors suggests a standard error for f I
of 3 to 4%. Two experimental determinations of known mixtures led, however, to errom of only 0.9 and 0.2%. ACKNOWLEDGMENT
The authors are indebted to A. G. Hastings and R. L. Grantham, Hughes Research Laboratories, for analyses of the two materials discussed in this paper. Electron micrographs of anatase and rutile particles were made with the collaboration of D. C. Pease. Anatomv Department, University of ’ California a t Los Angeles.
LITERATURE CITED
(1) Alexander, L., K I ~ H. ~ ,P., ANAL. CHEM.20, 886 (1948).
(2) Bum, C. W., J . Sa. Znstr. 18, 70 (1941). (3) Xlug, H. P., ANAL,CmM. 25, 704
,~”-”,. 1105?\
(4) Xlug, H. P., Alexander, L., “X-Ray Diffraction Procedures,” Wiley, New York, 1954. ( 5 ) Klug, H. P., Alexander, L., Kummer, E., ANAL. CHEM. 20, 607 (1948). (6) Legrand, C., Chimie et Industrie 68 360 (1952). (7) Rahm, J. A,, ANAL.CHEM.24, 1832 (1952).
R~~~~~~ for review September 17, 1956. Accepted December 31, 1956.
Steroid X-Ray Diffraction Powder Data JONATHAN PARSONS, WILLIAM T. BEHER, and GIZELLA D. BAKER The Edsel B. Ford Institute for Medical Research, Henry Ford Hospital, Detroit 2, Mich.
t X-ray diffraction .powder data and powder pattern photographs are presented for 32 steroids.
T.
o CONTINUE . . the studies on the identification of steroids by x-ray powder diffraction, 32 additional compounds were investigated. Their interspacing data and powder pattern photographs are here reported. The earlier papers (I-3) in this series gave powder data for 106steroids. The x-ray patterns were obtained in 5 hours, using nickel-filtered copper x-radiation produced a t a potential of 35 kv. and a current of 20 ma. (f,f?). The methods of recrystallization used were the same as those discussed and used in the last paper of this series (3). The majority of the steroids were recrystallized from ethyl alcohol, the exceptions being noted in Table I.
Figure 1. X-ray diffraction powder patterns of steroids
Key found
762
Table I
ANALYTICAL CHEMISTRY
Table 1.
Index to Steroid X-Ray Diffraction Powder Data
Pattern
No.
Melting Pooint (Uncorr.), C.
Name
I. CI8STEROIDS A1 A2 A3
257-261 167-169 251-256
Equilenin Estrone methyl ether 1-Methyl estrone
11. B. B1 B2
Monohydric Alcohols
Androstane-17-01 Neosterol (75.5y0 ergosterol and 24.5y0 A7,*2-ergostadien3p-01)~ C.
Cl C2 c3 c4 c5 C6
STEROIDS
A61'-Androstadiene-38, 17p-diolb A617-Androstadiene-3P,17p-diol-dibenzoate
17-Ethynyl-A6-androstene-3,17-diol A6-Androstene-3@,17-diol-diacetate A4-Cholestene-3pl6P-diol-diacetate Allopregnane-3& 20-diol-diacetate
Dec. 225-228 218-220 245-246 160-162 133.5-13s 141-145
Monoketones 155.5-157.5 103-106 115-120
A16-Allopregnene-20-one AI-Cholestene-3-one Androstane-17-one E.
El
164-168
Dihydric Alcohols
D. D1 D2 D3
164.5-166.5
Diketones
Allopregnane-3, 20-dione
202-205
F. Monohydroxymonoketones F1 F2 F3 F4
F5 F6 F7
F8
A4-Pregnene-20p-ol-3-one A4-Androstene-17-01-3-0ne-17-acetate-3-enol acetate (testosterone diacetate) A4-Androstene-17-ol-3-one-17-propionate-3-enol propionate (testosterone dipropionate)" Androstane-17-01-3-0ne-17-acetate (dihydrotestosterone acetate) Androstane-17p-ol-3-0ne-17-hexah drobenzoate (dihydrotestosterone hexahydrobenzoatey Pregnane-3p-ol-20-one-3-acetate Allopregnane-3~-ol-2O-one-3-acetate Etiocholane-l7p-ol-3-0ne-17-acetate
166-168 151-154 123-126 157-159 161-163 112-1 15 144-146 146-148
G. Dihydroxymonoketones GI G2
H. H1 H2
215-218.5 210-203.5
Pregnane-3q 17~~-diol-20-0ne Allopregnane-3, 21-diol-20-one-21-acetate Trihydroxymonoketones
A6-Pregnene-3p, 17, 21-triol-20-one-3,21-diacetate (17hydroxy-21-acetoxy pregnenolone acetate) Allopregnane-3p, 17a, 21-triol-20-one-2l-acetate"
267-270 231-235
111. BILE ACIDESTERS
I. Carboalkoxy Esters I1 I2
Methyl 3-acetoxy-12-ketocholanate Methyl 3-keto-12p-acetoxycholanate
145-148 118-119
IV. STEROIDAL SAPOGENINS A N D DERIVATIVES Jl 52 53
A4-Hexogenone Hecogenin Smilogenone
Dec. 233-235 261-262 181-186
Acetone. Ethyl alcohol and ethyl ether. Methanol.
VOL. 29, NO. 5, MAY 1957
763
Tab1, e II.
d , A. 1/11 I. Cle STEROIDS A l . Equilenin 12 4 0 11 7 00 0 06 6 44 5 65 5 17 4 82 4 44 4 18 3 72 3 32 3 21 3 08 2 96 2 78 2 59 2 48 2 41 2 35 2 27 2 22 2 17 2 12 2 05 1 96 1 91 1 85 1 80 1 73
0 20 0 03 1 00 0 06 0 06 0 06 0 53 0 20 0 06 0 03 0 03 0 04 0 01 0 03 0 04 0 06 0 01 0 01 0 01 0 04 0 03 0 03 0 01 0 01 0 01 0 01
A2. Estrone Methyl Ether 9 16 0 06 7 31 0 04 6 52 0 03 5 79 1 00 5 07 0 40 4 60 0 11 3 40 0 20 4 06 0 11 3 82 0 01 3 64 0 03 3 44 0 53 3 33 0 20 3 13 0 04 2 97 0 15 2 87 0 06 2 71 0 11 2 60 0 11 0 I1 2 50 2 41 0 06 2 31 0 08 2 27 0 08 2 22 0 11 2 18 0 08 2 15 0 11 2 11 0 04 2 04 0 08 1 95 0 06 1 92 0 08 1 87 0 06 1 82 0 04
A3
8 8 6 6 6 5 5 4 4 4 4
764
I-Methi1 Estrone 68 0 03 12 0 38 71 0 56 35 0 05 01 0 05 54 0 75 35 0 08 90 1 00 50 0 08 30 0 08 05 0 38
I/Ii
d , A.
X-Ray Diffraction Powder Data for Steroids
A3. 1-Methyl Estrone (Contd.) 3.87 0.56 3 68 0.15 3 38 0.28 3 25 0.28 3.14 0.03 3.08 0.20 2.98 0.20 2 89 0 11 2 76 0 01 2 63 0 15 2 53 0 11 2 46 0 05 2.40 0.20 2.35 0.1; 2.30 0.15 2.23 0.05 2.15 0.20 2.09 0.08 2.03 0.08 1.96 0.15 1.93 0.11 1.86 0.15 1.79 0.20
B2.
STER-
C.
11.
OIDS
B.
B1. 12 9 7 6 5
5 5 4 4 4
Monohydric Alcohols Androstane17-01 8 0 05 8i 0 05 53 0 41 54 0 73 83 1 00 54 0 55 02 0 73 76 0 55 29 0 27 01 0 20
3 65 3 44 3 32 3 19 3 08 3 00 2 73 2 63 2 53 2 45 2 36 2 21 2.14 2 09 1 98 1 90 I 81 1 77
0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0
15 05 05 20 05 05 20 11 08 08 02 20 08 I1 08 08 02 02
B2. Seosterol 13.3 0.08 11.4 0.11 9.51 0.01 6.82 0.01 6 15 0 73 5 80 0 53 5 31 I 00 5 04 0 63 4 e2 0 20 4 31 0 87 4 14 0 11 3 93 0 30 3 80 0 06
ANALYTICAL CHEMISTRY
I/Ii
d , A.
n'eosterol
(Contd.) 3.64 3.42 3.28 3.00 2.94 2.87 2.i8 2.73 2.67 2.43 2.36 2.29 2.21 2.18 2.12 2.08 2.02 1.97 1.93 1.85 1.77 1.72
0.06 0.35 0.30 0.08 0.08 0.11 0.08 0.08 0.15 0.04 0.06 0.15 0.04 0.15 0.01 0.08 0.03 0.03 0.11 0.04 0.04 0.06
Dihydric Alcohols c 1 . A5b7Androstadiene38, 17p-diol 14.3 0.05 i2 5 o 05 8 35 0 08 7 44 0 11 6.17 0.11 5.82 0.08 5.47 1.00 5,2l 1 00 4.90 0.08 4.75 1.00 4.25 0.55 3.91 0.11 3.75 0.11 3 62 0 05 3 35 0 27 3 09 0 20 3 01 0 20 2.92 0.11 2.73 0.08 2.49 0.11 2.34 0.03 2.25 0 05 2.17 0.05 2.03 0.08 1.80 0.08
c 2 . A5'7dndrostadiene3p,17B-diol dibenzoat,e 12.3 0.08 8.27 0.15 6.61 0.06 6.03 0.i3 5.51 1.00 4.98 0.40 4.58 0.25 4.17 1.00 3.96 0.30 3.76 0.17 3.60 0.17 3.41 0.06 3.25 0.46 3.14 0.11 3.01 0.25 2.92 0.04 2.83 0.11
d , A. 1/11 1/11 d , A. 1/11 C2. Ass7C4. A6D. Monoketones AndrostadieneAndrostene-3p,l7D1. AI63p,17p-diol diol diacetate (Contd.) Bllopregnenedibenzoate (Contd.) 2 , i4 o, 20-one 2.75 0.15 2.64 0.15 1 1 . 8 0.27 2.68 0.11 2.54 0.10 10.4 0.04 2.59 0.20 2.40 0.15 8.31 0.01 2.49 0.08 2.32 0.15 6.21 0.27 2.40 0.34 2.30 0.15 5.57 1.00 2.31 0.04 2.13 0.03 5.08 0.11 2.26 0.04 2.02 0.10 4.65 0.08 2.20 0.04 1.98 0.07 4.24 0.40 2.14 0.06 1.91 0.10 4.06 0.15 2.11 0.11 1.86 0.03 3.78 0.05 2.07 0.06 3.65 0.15 2.04 0.06 3.38 0.04 3.28 0.20 c5. 343.18 0.11 3.08 0.08 2holestene-38,6pdiol diacetate 2.89 0.11 C3. 17-Ethynyl2.72 0.04 A6-androstene15.6 0.06 2.65 0.05 3,17-diol 12.5 0.08 2.55 0.02 10.8 0.11 12.1 0.06 2.39 0.05 8.98 0.01 10.6 0.04 2.29 0.08 7.73 0.08 8.51 0.15 2.19 0.11 7 03 o ii 6.44 0.40 2.12 0.05 6 26 0 40 5.74 1.00 2.08 0.05 5.75 0 04 5.21 0.20 2.03 0.04 5.29 0 04 4 76 0 25 1.86 0.01 5.21 1.00 4 52 0 13 1.80 0.02 4.76 0.11 4 30 0 53 1.64 0.01 4.39 0.01 4 12 0 30 4 32 0 20 3.86 0.18 3.85 0 08 3 75 0 11 3 68 0 15 3.56 0 03 D2. 31-Cholestene3 54 0 04 3 36 0 06 3-0ne 3 38 0 04 3 24 0 20 3 24 0 03 12.8 0.08 3 10 0 15 3 15 0 01 9.56 0.30 2.94 0.11 2 83 0 01 8.72 0.11 2.86 0.04 2 70 0 02 7.87 0.11 2.79 0.20 2 55 0 02 6.i4 0.35 2.67 0.15 2 37 n ni 6.03 0.01 2.60 0.08 2 32 0 03 5.49 1.00 2.49 0.10 2 23 0.02 4.98 0.73 2.41 0.08 2.17 0.03 4.70 0.30 2.35 0.10 4.30 0.30 2.26 0.08 3.97 0.08 2 20 0.08 3.64 0.20 2.15 0.15 3.38 0.01 2.12 0.13 C6. Allopregnane3.22 0.15 2.08 0.13 38,20-diol diacetate 3.10 0.11 2 02 0 08 16.5 0 03 2.93 0.04 1 95 0 04 10.7 0.04 2.77 0.03 1 89 0 01 8.89 0.15 2.66 0.03 1.86 0.11 7.22 0.20 2.53 0.15 6.17 1.00 2.46 0.06 5.80 0.30 2.39 0.01 5.57 0.40 2.31 0.04 5.37 0.20 2.25 0.04 C4. A64.98 0.40 Androstene-3n,174.56 0.20 diol diacetate 4.35 0.15 4.20 0.11 14.7 0.27 D3. dndrostane3.86 0.30 7.40 0.27 17-0ne 3.61 0.08 6.89 0.03 9 31 0 15 3.36 0 04 5 93 1.00 6 24 0 30 3.04 0.11 5 85 0 40 2.90 0.08 5 54 1 00 2.81 0.11 5 23 0 20 2.67 0.01 4 82 1 00 2.61 0.04 4 6i 0 08 2.52 0.06 4 11 0 08 2.44 0.08 3 76 0.10 3 84 0 04 2.30 0.04 3 64 0 15 3 51 0 15 2.18 0.06 3 51 0 20 3 35 0 20 2.10 0.06 3 42 0 15 3 19 0 30 2.07 0.01 3 32 0 20 3 00 0 15 1.97 0.03 3 20 0 10 2 94 0 06 1.86 0.01 2 92 0 15 2 85 0 08 1.75 0.04 2 84 0 10 ntinued o n page 765) d , A.
Table II.
d , il. 1/11 D3. Androstane17-one (Contd.) 2.7i 0.08 2.59 2.50 2.36 2.32 2.24 2.15 2.08 2.05 1.98 I .94 1.88 1.79 1.77
0.08 0.04 0 11 0.11 0.06 0 06 0 08 0 08 0.04 0 04 0 06 0 04 0 01
E. Diketones
El. Allopregnane3,20-dione 10.9 0.04 6.00 0.40 5.91 0.30 5.59 1.00 5.11 0.30 4.54 0.03 4.34 0 08 4.12 0.08 3.72 0.04 3.58 0.04 3.42 0.03 3.29 0.04 3.21 0.20 3.11 0.15 3.01 0.06 2.87 0 08 2.76 0 06 2.67 0 06 2.58 0.08 2.48 o.oi 2.37 0.08 2.28 0.03 2.17 0.04 2.10 0.04 2.03 0.01 1.96 0.06 1.80 0.01 3.68 0.01
F. Monohydroxymonoketones F1.
A‘-Pregnene208-01-3-one 13.2 0.27 10.0 0.09 8.15 0.09 7.37 0.36 5.89 1.00 4.93 0.67 4.70 0.27 4.53 0.04 4.08 0.20 3.80 0.20 3.62 0.09 3.42 0.04 3.32 0.09 3.09 0.02 3.00 0.20 2.68 0.02 2.48 0.04 2.44 0.13 2.31 0.04 2.22 0.13 2.07 0.09
d, A 1/11 F2. A4-Androstene17-01-3-one-17acetate-3-enol acetate 14.2 0.27 8.47 0.05 7.47 0.55 5.83 1.00 5.32 0.27 4.88 0.15 4.72 0.73 4.52 0.27 4.33 0.05 3.93 0.41 3.71 0.20 3.51 0.27 3.35 0.11 3.25 0.20 2.90 0.20 2.78 0.20 2.60 0.15 2.45 0.04 2.35 0.15 2.24 0.15 2.16 0.08 2.09 0.05 2.01 0.11 1.96 0.11 1.82 0.04 1.64 0.02
X,-Ray Diffraction Pow ler Data for Steroids (Continued) d, A. 1/11 d , 4. 1/11 d, A. 1/11 F6. PregnaneG. DihydroxyF4. Androstane-
F3. A4-Androstene17 01-3-one-17propionate-3-enol propionate 14.3 0.05 7.97 0.27 7.14 0.11 0.27 6 11 5.76 1.00 5.55 0.08 4.76 0.73 4.53 0.27 4.32 0.02 4.04 0.20 3.95 0.55 3.76 0.08 3.63 0.15 3.51 0.15 3.37 0.11 3 20 0.04 3.09 0.02 2.91 0.11 2.77 0.15 2.65 o.ii 2.56 0.04 2.49 0.08 2.37 0.08 2.26 0.20 2.18 0.02 2.05 0.05 1.99 0.05 1.90 0.04 1.84 0.04 1.75 0 01 1.71 0.02 1.70 0.02
F4. androstane17-01-3-one-17acetate 15.0 0.20 9.98 0.04 7.70 0.04 6.13 0.27 5.49 0.27 5.14 0.20
l7-ol-3-one- 17acetate (Contd.) 4 27 1 00 3 75 0 08 3 48 0 01 3 08 0 08 2 74 0 15 2 51 0 08 2 37 0 04 2 21 0 03 2 05 0 03
F5. Androstane178-01-3-one 17hexahydrobenzoate 12.1 0.15 10.8 0.15 1.00 6.49 0.40 5.99 5.49 0.87 5.02 1.00 4 65 0 20 0 23 4 09 3 87 0 17 3 73 0 15 3.60 0.15 3.49 0.20 3.28 0.11 3.09 0.35 3.01 0.30 2.90 0.06 2.78 0.23 2.62 0.20 2.41 0.15 2.34 0 11 2.30 0.11 2.22 0.11 2.17 0.15 2.12 0 04 2.08 0.15 2.02 0.08 1.98 0.08 1.91 0.15
F6. Pregnane3.B-01-20-one-3acetate 9.51 0.15 7.22 0.05 6.57 1.00 5.78 0.08 5.51 0.21 5.15 0.73 4.S4 0.08 4.54 0.08 4.31 0.41 4.03 0.11 3.92 0.11 3.68 0.15 3.59 0.15 3.43 0.20 3.29 0.15 3.23 0.11 2.99 0.15 2.88 0.11 2.78 0.05 2.66 0.11 2 57 0.15 2.41 0.11 2 36 0.11 2.28 0.11 2.19 0.08 2.16 0.11 2.11 0.15 2.02 0.20 1.95 0.08
3p-01-20-one-3acetate (Contd.) 1.8; 0.02 1.81 0.04 1.78 0.05
F7. Allopregnane3.B-ol-20-one-3acetate 13.3 0.20 10.3 0.11 7.94 0.06 7 34 0.11 6 74 0.11 6.07 1.00 5.55 0.73 4.94 0.30 4 68 0.73 4.39 0.30 4.16 0 30 3 95 0 20 3 82 0 20 3 69 0 08 3 54 0 08 3 30 0 20 3.16 0.08 2.97 0.06 2.80 0.06 2.63 0.08 2.56 0.08 2.46 0.15 2.36 0.04 2.33 0 03 2.26 0 08 2.18 0.08 2 00 0.06 1.91 0.06 1.88 0.01 1.83 0.01 1.76 0.01
F8. Etiocholane178-01-3-one-17acetate 15.1 0.09 8.08 0.09 7.37 0.27 6.59 0.37 6.01 1 00 5.80 0.49 5 54 0 49 5 18 0.27 4.88 0.49 4.40 0.36 4.12 0.49 3.90 0.27 3.75 0.13 3.63 0.36 3.37 0.09 3.1? 0.09 2.97 0.04 2 91 0.13 2 63 0 27 2 50 0 04 2 43 0 04 2 34 0 13 2 33 0 04 2 18 0 09 2.11 0.09 2.00 0.20 1.94 0.04 1.88 0.04
d, A. 1/11 A6-Pregnene3p, 17,21-triol-20one-3,21-diacetate (Contd .) 3.51 0.04 3.29 0.08 3.16 0.08 3 05 0 05 2 99 0 41 2 85 0 15 2 73 0 15 2 67 0 15 2 57 0 04 2.50 0.04 2.43 0.13 2.40 0.13 2.36 0.13 2.28 0.15 2.lj 0.04 2.OR 0.20 2.03 o 13 1.98 0 05 1 93 0.13 1 84 0.08
H 1.
monoketones G1. Pregnane3n,l 7a-diol-20-one 10 5 0 06 6.84 0 15 6.40 0 04 5.80 1.00 5.61 0 03 5.28 0.20 5.14 0.15 4.76 0.15 4 46 0 08 4 18 0 08 3.86 0 11 3 65 0.15 3 43 0 15 3 20 0 06 2 ’44 0 06 2 82 0 06 2 72 0 08 2 62 0 08 2 54 0 11 2 36 0 04 2 1T 0 04 2 14 0 06 2.02 0 03 1 92 0 03 1.89 0.03 G2. Allopregnane3,21-diol-20-one21-acetate 9.66 0 27 8.94 0 24 6 61 0.05 6 37 0 08 5 84 1 00 5.17 0 08 4.85 0 73 4.27 0.15 4.11 0.15 3.96 0.15 3.83 0.04 3.65 0.11 3.52 0.04 3.29 0.20 2.99 0.20 2.82 0.04 2.69 0.15 2.59 0.08 2.54 0.11 2.47 0.04 2.34 0.04 2.29 0.02 2.22 0.11 2.17 0.02 2.10 0.05 2.05 0.05 1.98 0.15 1.88 0 08 1.81 0.02 1.75 0.02 1.67 0.05 H . Trihydroxymonoketones H1. A5-Pregnene38, li,2l-triol-20one-3,al-diacetate
H2. Allopregnane3p,17a,2l-triol-20one-21-acetate 11.9 0.15 8.35 0.11 7.23 0.20 6 4i 0 11 5 99 1 00 5 65 0 40 5.51 0 15 5 10 0 40 4 94 0.08 4 56 0.40 3 39 0 15 3 97 0 15 3 78 0.20 3 58 0 15 3 30 0 06 3 13 0 08 3.00 0.30
1.87 1.83
0.08 0.06
111. BILE ACID ESTERS
I. Carboalkoxy esters
11. Methyl 3-acetoxp-12ketocholanate 14.5 0 06
(Continued on page 766)
VOL. 29, NO. 5 , MAY 1957
765
d, A.
1/11 11. Methyl 3-acetoxy-12ket,ocholanate (Contd.) 3.72 3.52 3.34 3.12 3.01 2.85 2.72 2.64 2.57 2.47 2.34 2.28 2.21 2.05 2.02
0.30 0.17 0.20 0.11 0.06 0.11 0.03 0.15 0.01 0.08 0.03 0.04 0.04 0.11 0.11
12. Methyl 3-keto-
lap-acetoxycholanate
12.4 10.9 9.66 8.76 6.92 6.64 6.01 5.49 5.29 5.15 4.60
0.15 0.07 0.01 0.75 0.37 1.00 0.20 0.20 0.50 0.50 0.27
Table II. X-Ray Diffraction Powder Data for Steroids (Continued) d, A. Z/Ii d, A. 1/11 d, A. 1/11 d , A. I/Il d, A. 1/11 12. Methyl 3-keto53. Smilogenone (Cont.) J1. A4-Hecogenone 52. Hecogenin 12D-acetoxy(Contd.) (Contd.) 0.08 0.15 2.08 2.75 cholanate (Contd.) 0.15 0.15 2.00 3.42 0.06 2.60 4.16 0.27 2.58 0.08 1.93 0.04 4.08 3.90 0.20 0.20 3.10 0.20 0.06 0.06 1.88 2.36 3.94 3.69 0.37 0.10 2.99 0.06 0.01 0.08 1.82 2.31 3.73 3.62 0.15 0.37 2.81 0.04 1.76 0.04 2.17 0.06 3.62 3.46 0.15 2.72 0.11 0.10 3.50 0.27 3.36 0.20 2.52 0.08 3.33 0.07 2.47 0.06 0.03 3.10 3.16 0.20 2.95 0.15 2.40 0.04 3.03 2.82 0.03 0.10 2.34 0.08 2.88 0.15 2.66 0.15 2.30 0.08 ACKNOWLEDGMENT 2.74 0.07 2.57 0.10 2.23 0.08 2.65 0.07 2.45 0.05 2.16 0.04 The authors are indebted to Carl 2.54 2.34 0.10 0.10 2.09 0.08 2.40 2.22 0.10 0.07 Djerassi, Chemistry Department, 2.03 0.04 2.31 2.17 0.10 0.07 1.92 0.01 Wayne State University, Detroit, who 2.17 0.10 2.08 0.10 1.86 0.03 kindly donated the steroids used in 2.10 0.07 1.99 0.05 this study. They also wish to thank 2.01 1.96 0.10 0.15 53. Smilogenone 1.98 0.15 Dorothy Hebert for technical assistance. 15.8 0.11 52. Hecogenin 9.26 0.30 IV. STEROIDAL 15.0 0.20 7.22 0.30 AND SAPOGENINS 11.1 0.03 6.84 0.20 LITERATURE CITED DERIVATIVES 8.23 0.11 5.87 1.00 7.20 0 . 0 3 5.59 0.20 J1. A4-Hecogenone (1) Beher, W. T., Parsons, J., Baker. 5.99 0.11 5,3l 1.00 G. D., ANAL. CHEM. 27, 1569 13.6 0.15 5.54 1.00 5.08 0.30 (1955). 6.89 0.20 5.0i 0.11 4.64 0.40 (2) Parsons, J., Beher, W. T., Zbid., 27, 6.22 0.20 4.73 0.11 4.29 0.20 514 (1955). 5.84 1.00 4.42 0 20 3.96 0.20 (3) Parsons, J., Beher, W. T., Baker, G. 5.39 0.20 4.24 0.08 3.56 0.30 D., Zbid., 28, 1514 (1956). 5.17 0.37 3.30 0.11 4.00 0.08 3.11 0 1.5 4.93 0.37 3.77 0.11 4.67 0.37 3.62 0.08 2.88 o.i5 RECEIVED for revien November 27, 1956. Accepted December 13, 1956.
Monochromatic Diff raction-Absorption Technique for Direct Quantitative X-Ray Analysis D. H. LENNOX Occupafional Health Division, Department of Nafional Healfh and Welfare, Ottawa, Canada
b In a diffraction-absorption method of quantitative x-ray analysis, a polychromatic beam was employed for the absorption measurement. Use of a polychromatic beam limits the precision and may introduce large errors. An alternative method, employing an essentially monochromatic beam, which eliminates these difficulties, is reported. A number of known samples were analyzed by the diffraction-absorption methods and by the internal standard. It is concluded that the diffraction-absorption methods are reproducible and capable of giving results comparable to those obtained with the internal standard; for some problems, they may provide the only suitable method of analysis.
766
ANALYTICAL CHEMISTRY
A
of direct quantitative xray analysis for a-quartz, using a Norelco diffractometer (79, was developed as a n alternative to the commonly used internal standard technique (2, 3). -4 general theoretical equation was derived, expressing concentration as a function of diffracted intensity and x-ray absorption: m m o D
where
I1 = integrated intensity diffracted by a sample with mass absorption coefficient p: containing weight fraction z1 of component 1 (I& = integrated intensity diffracted by a sample with mass absorption coefficient p: comprised wholly of component 1
A similar equation was found to hold experimentally. The measured diffracted beams were, of course, essentially monochromatic, but absorption measurements were made employing the polychromatic beam emitted by a copper target x-ray tube. For simplicity, this method is here called the polychromatic diffraction-absorption technique. A monochromatic technique using the beam diffracted by a crystal monochromator for absorption measurements is also a possibility. I n this case, however, the measurable x-ray absorption range is smaller and it was believed to be too small for practical a-quartz analysis. Experience with the polychromatic technique has since indicated that the range of absorption met in practice is not excessively large.
