The condensate of the niain stream smoke of 260 long-size popular American nonfilter cigarettes was obtained in a fully automatic Ethel Mark VI smoking machine designed by Cigarette Components Ltd., of England. The part for the electrostatic precipitation of this machine was replaced by a cool-trap system for the collection of the condensate (trap 1, outside cooled by ice water; trap 2, by dry ice-acetone). All cigarettes were ignited n-ith an electric lighter and smoked with a 35-ml. puff volume for 2 seconds every minute to a butt length of 23 mm. Before the analysis, the condensate was dried to constant weight over calcium chloride (7.32 grams). The separation is shown in Figure 1. The nitromethane e.xtract (0.82 gram) was chromatographed on 30 grams of silica gel (deactivated) ( 2 ) . Hexane was used for elution from fraction I through fraction VII, hexane and benzene (4 to 1) for fractions VI11 to X. Fractions I1 to VJII are named according to their major polycyclic hydro-
188.
carbon constituents. This does not exclude the presence of minute quantities of these hydrocarbons in the neighboring fractions. Benzo(a)pyrene, for instance, was found not only in fraction VI but also in small amounts in fractions V and VII. The corresponding bands from the paper chromatography fractions n-ere combined and rechromatographed for further purification. In the case of benzo(a)pyrene only two chromatograms were usually necessary to obtain identical fluorescence and ultraviolet absorption spectra down to 250 mp by comparison with the authentic hydrocarbon. The loss of benzo(a)pyrene by the use of this method of separation amounts to about 30% as proved by the tracer technique ( 2 ) . From the smoke condensate 5.5 y of benzo(a)pyrene (0.75 p.p.m.) was isolated. The tracer method indicated a total of 7.9 y of benzo(a)pyrene (1.1 0.1 p.p,m.) to be actually present. Fluoranthene, pyrene, alkylpyrene,
*
chrysene, and alkylchrysene were found in the same amount as determined by the former method ( 2 ) . For the detection of benzofluoranthenes, bemanthracene, dibenzanthracene, benzo(e)pyrene, benzoperylene, and perylene we started with twice the amount of smoke condensate as used for the determination of benzo(a)pyrene. LITERATURE CITED
(1) Grimmer, Gernot, personal communi-
cation.
(2). Hoffmann, D., Wynder, E. L., “Isolation and Identification of Polynuclear Aromatic Hydrocarbons,” Cancer, in
press.
DIETRICHHOFFMANN ERNEST L. WYNDER
Section of Epidemiology Division of Preventive Medicine Sloan-Kettering Institute New York, N. Y.
Aluminum Boride, AIBlP
J. A. KOHN and D. W. ECKART, U. S. Army Signal Research and Development Laboratory, Fort Monmouth, N. J. postulating vacant sites in the structure; ALPHA-PHASE The powder diffraction data tabulated our data would necessitate -20 unbelow were obtained using filtered RYSTALS of a-A1BI2, as well as occupied sites per unit cell ( 4 ) ] . copper radiation with a Geiger diffracthose of D-AlBl2 (see next Formula Weight. 156.82. tometer. Single crystal diffraction insection), were recovered from the reac0.003 grams per Density. 2.557 tensities were used to assist in the tion products of two different methods cc. (pycnometric in toluene). indexing of the powder lines, where of preparation. The first was a simple two or more calculated spacings showed melt reaction, using the elements; PROPER TIE^ OPTICAL equally suitable agreement. Refractive Indices. w and e > 2.20 the second was an aluminothermic (by freezing in PbC12). reaction, using elemental aluminum Absorption Edge. Approximately and B2O8. Boride crystals were sepaCRYSTAL MORPHOLOGY 6500 A. (calculated energy gap, 1.8 to rated in each case by leaching with dilute Crystal System and Class. Tetrag1.9 e.v.). aqua regia. Both methods of preparaonal, pseudocubic [true symmetry first described by Halla and Weil @)I; tion have been described in detail (4). FUSION BEHAVIOR tetragonal trapezohedra1 class. Crystals of a-AlB12 were obtained Melting Point. 2150’ =t 50’ C. Form and Habit. Platelike along as tetragonal (pseudocubic), hematite(in helium at 50 p.s.i.). (101) = (111) cubic; crystals are like plates, up to 2 mm. in largest Oxidation Temperature. 700” C. essentially pseudooctahedrons, most of dimension. Very thin sections were them flattened along (111) of the wine-red to orange-red in strong transpseudocubic cell; forms observed are BETA-PHASE mitted light. This phase was first first-order prism ( 1101, ditetragonal Crystals of &4.lBI2 were obtained described in the early literature as a prism ( 3201, first-order bipyramid from the same reaction products as form of elemental boron, having been { 1111, second-order bipyramids ( 101) were those of &-AlBl2. Specimens were and { 201 ) , and tetragonal trapezotermed “graphite-like boron” (6). It hedrons (312) and { 314) ; { 101) is by orthorhombic (pseudotetragonal) biwas later shown to be aluminum boride, far most common, with (110) next; pyramids, up to 2 111111. in largest dimenMBiz (3). twinning on (101) is fairly common. sion, translucent to opaque, ranging in X-ray diffraction studies were carried Axial Ratio. c : a = 1.4050:l color from yellow to honey-yellow to out with copper radiation, using rota(morph.); 1.4057: 1 (x-ray). amber to brown. Until relatively retion and Weissenberg methods for cently (b), this phase was considered a single crystals and powder film and X-RAYDIFFRACTION DATA form of elemental boron (termed diffractometer techniques for polycrysSpace Group. P41212 or enantio“adamantine or diamond-like boron”) talline specimens. The Weissenberg morphous P4&2. or possibly a ternary borocarbide (1). patterns showed the following systemCell Dimensions. a = 10.161 f X-ray diffraction studies were carried atic absences: 001 with I # 4n; 0.001 A , ; c = 14.283 f 0.002 A. out using the same techniques as hOO, with h # 2n. This permitted an [a = 10.28 A.; c = 14.30 A. ( S ) ] . described for a-AIBlz. Weissenberg unambiguous determination of the space Formula Weights per Cell. 14.4 patterns showed the following systemgroup as P41212 (or enantiomorphous [Halla and Weil (2) explained this atic absences: hkl, with h k 1 # 2n; deviation from a reasonable integer by P43212).
C
*
+ +
296
ANALYTICAL CHEMISTRY
X-Ray Powder Diffraction Data for a-AIB1* I/I!b h k 1 d( Calcd.)a d(0bsd.) I/I,b 1 d( Calcd.)o d(0bsd.) 8.29 3 2 1 5 2.419 2.420 1 8.28 21 27 3 3 0 7.17 2,395 7.18 29 2.394 0 33 1 6.43 2.362 6.42 2.362 5 17 1 4 1 2 2.330 2.334 13 0 5.08 5.07 42 4 0 3 2 5.06) 2.240 34 2 2 5 1 8 4.79 4.79 4 1 3 4.54 7 2.189 2.189 0 4.54 11 4 2 2 2.165 2.164 28 2 1 1 4.33 68 2.140 3 3 3 1 0 3 2.136 19 31 5 2.135) 4.13 100 2 0 2 4.14 22 4 2 3 2.051 2.051 11 3 3.96 3.97 28 2.032 4 3 0 82 3.82 2 1 2 2.033 3.83 16 4 1 4 10 2.028 3.587 2 2 0 2.028 3.593 20 5 0 2.012 1 3.574 0 0 4 8 2.013 3.571 33 3 3 4 1.989 21 1.987 2 2 1 3.484 5 1 1 1.974 1.975 3.483 28 11 2 0 3 3,474) 1.955 4 3 2 8 1.955 51 2 14 1.919 22 3.285 2 1 3 1.918 3.287 1.898 4 0 5 1.897 11 2 2 2 30 3.207 5 2 1 11 4 1.871 1,870 13 4 3 3 1.869) 12 3.132 3 1 1 3.135 2 1 7 1.861 3 0 2 3.058 38 1.860 12 3 060 5 1 3 1.838 1 839 38 3 1 2 2.9307 1.766 4 3 4 2.927 1.766 15 21 2 0 4 2.921) 5 2 3 1.754 1.754 11 2.882 53 1 I.730 7 2 2 3 1 731 17 2.883 5 3 2 1,693 3 2 0 2.819 6 1.693 2.818 23 6 0 1 1.682 20 2 1 4 2.806 1.681 14 2.808 6 1 1 3 2 1 1.659’ 2.7651. 2.764 1.657 17 9 4 3 5 1.656] 3 0 3 2.760/ 1.636 1,636 5 3 3 3 1 3 2,663’1 8 22 2,657 6 2 1 1.597 1.599 11 5 4 2.6551 3 2 2 3 0 8 I ,579‘ 2,622 2.622 24 1.579 7 5 4 1 1,5771 2.539 12 4 0 0 2,540 2.533 2 2 4 11 2.533 4 3 6 1.546 1.546 11 2,501 4 0 1 17 2.501 6 3 0 1.515 2.488 28 2 0 5 2.490 I.514 5 6 1 4 1,513) 4 1 0 2.464) 2.460 19 5 5 3 1.48; 6 1.488 3 0 4 2.457, 6 3 2 1.482 1,482 6 2.425 2.425 34 3 2 3 5 2 6 1.479 1.479 8 Li Calculated on an LGP-30 digital computer, using single crystal cell dimensions and A = Peak heights on diffractometer trace; strongest line = 100.
h k 1 0 11 11 2 0 11 2 0 2 1
h 0 0 2 2 2 1 0 2 2 0 1 3 4 1 2 4 2 4 0 2
k l 1 1 2 0 0 0 1 1 2 0 1 2 2 2 0 2 3 1 4 0 3 2 1 2 0 0 2 3 1 3 1 1 4 0 2 0 4 4 4 2
d(Calcd.)O 7.92 6.32 6.1T 4.87 1.41?
d(0bsd.) 7.90 6.32 6.16 4.87
7 20 26 9
X-Ray Powder Diffraction Data for P-AIBI2 d( Calcd.)a d(0bsd.) I / I , b 1 3 4 2.142 2.143 6 0 6 0 2.105 2.106 3 6 0 0 2.057 2.052 4 1 6 1 2.033 2.030 2 2 6 0 1.992 1.994 15 3 5 2 1.982 1,981 24 1.961 4 0 4 1.960 26 0 6 2 1.945 1,947 14 6 0 2 1.910 1.910 11 2 4 4 1.885 1,885 17 4 2 4 1.873 1,873 12 1 5 4 1.773 1.773 7 5 5 2 1.666 15 4 4 4 4 6 2 1.645 1.644 11 6 4 2 1.632 1.633 11 0 6 4 1.621 1,622 4 6 0 4 1.598 1.597 3 2 2 6 1.581 1.577 9 4 3 5 1.574)
4.41 17 4.401 3.96i 3.93 70 3.921 3.291 3,289 5 3,138 3.161 11 3.136 3.130 21 3.099) 12 3.0851 3.092 s 2.901 2.900 3 2,890 2.888 4 2.874 2.871 20 2.811 2.809 14 2.772 2.768 2.540 2.543 23 27 2.460 2.460 4 2 2 2.433! 3 7 2 1.571 1.571 100 2.4321 3 4 1 2*431 8 0 0 1.543 1,546 12 2 7 3 1.542 1,541 0 2 4 2,357 2.356 12 1 7 4 1,461 1.461 2 0 4 2.349 2.350 4 2 4 6 1.451 1.451 2 5 1 2.278 2.281 4 4 0 2.207 2.207 9 5 6 3 1.446 2 2 4 2.202 2.203 7 4 2 6 Calculated on an LGP-30 digital computer, using single crystal cell dimensions * Peak heights on dzractometer trace; strongeet line = 100. 0
;:E)
7
7
4 8
8 21 and X
=
h k 1 6 0 5 4 1 8 7 0 1 3 3 8 5 1 7 53 6 6 4 1 1 1 10 6 2 5 7 2 0 6 3 4 2 0 10 7 2 2 6 1 6
d(Ca1cd.). 1.457 1,446’; 1.4441 1.431 1.426 1.406
;:E) 1.400 1.396‘ 1.395) 1.375 1.370 1.367
d( Obsd.) 1.457
7
1.445
22
1.432 1.426 1.407
16 10 11
1.401
13
1.399
19
1.395
17
1.374 1.370 1.367
10 7 17
1.333
20
1.3031 1.2997 1,2951 1.2836 1.2513 1.2468
10 13 10 6 9 4
4 5 6 7 6 5 5 5
1 5 0 2 5 5 0 3
9 4 7 4 1 5 9 8
1.334’1 1.3333 1,3031 1.3000 1.2956 1,2837 1,2508 1,2471
7 7 2 7 5 7 8
4 0 2 4 4 5 2
2 6 11 3
1.2398
8
8
1,24111 1,23931 1,2211 1,2184 1,1861
1.2209 1.2184 1.1865
6 9 4
2 4
1,1654’1 1.1648j
1.1652
5
8 7 6 3
3 4 5 3
3 5 6 11
1,1538‘) 1,1531,
1.1533
5
1.1416’1 1.1411)
1.1416
4
6 2 9 8 3 4
I,1290‘
1.1288
4
1.1209
8
1,1283)
7 5 4 1.1214” 8 0 6 1,12061 1.54050 A. ( C u K a l ) .
h k l d( Calcd.). 6 1 5 1.436’1 4 6 4 1.435! 6 4 4 1.426 4 8 0 1,405 8 4 0 1,386’ 3 7 4 1.385,’ 7 3 4 1.369 6 3 5 1.367 1 9 2 1.345‘ 4 4 6 1.344,’ 0 6 6 1.320 6 0 6 1 ,3073 1,3064) 4 1 7 8 5 1 1,3056; 8 2 4 1.2906: 2 6 6 1,29041 3 9 2 1.2851 0 0 8 1,2701 9 3 2 1.2628 6 5 5 1.2547‘ 1,2539) 4 3 7 4 8 4 1.2298 2 2 8 1.2206 4 6 6 1.2139 1.54050 -4.(CuKai).
d(0bsd.)
I/I,b
1.436
6
1.425 1.405
5 10
1.385
11
1.368 1.366
10
1.345
3
1.321 1.3075
6 3
1.3060
3
1.2901
4
1.2843 1.2706 1,2621
4 2 4
1.2547
5
1.2296 1.2213 1.2132
5 5
VOL. 32, NO. 2, FEBRUARY 1960
-
3
297
{ O l O ) , macropinacoid { loo}, and basal pinacoid { O O l ) ; (1011 and (011) are most predominant. Polysynthetic twinning on (110) and (170). Axial Ratio. a : b : c = 0.9750:l: 0.8045 (x-ray) ; not determined morphologically owing to multiple reflections caused by twinning.
hkO, with h # 2n. The corresponding space group is I 2/m 2/m 2/a. The literature space group is given as tetragonal P 4/nnm or a subgroup ( 5 ) . All Weissenberg patterns showed twinning on both (110) and (lio). Observations with a n electron microscope showed the twinning to consist of two sets of extremely fine, multiple, parallel layers. The latter were approximately 2000 A. in thickness, giving rise to continuous visible spectra on the crystal faces when these vvere viewed with an optical microscope. Tabulated powder diffraction data n-ere derived in the same manner as for a-A1Bl2.
X-RAYDIFFRACTION DATA Space Group. I 2 / m 2/m 2/a [tetragonal P 4/nnm or a subgroup (5)1. Cell Dimensions. a = 12.34 & 0.01 A , ; b = 12.631 & 0.005 A.; c = 10.161 =t 0.001 A. [Tetragonal, a = 12.55 A.; c = 10.18A. ( 5 ) ] . Formula Weights per Cell. 15.8. Formula Weight. 156.82. 0.003 grams per Density. 2.600 cc. (pycnometric in toluene).
FUSIOS BEHAVIOR Melting Point. 2200 helium a t 50 p.s.i.1.
D. E. NICHOLSON, Humble O i l 8 Refinina- Co.,. Bavtown, . , lex.
I
*
50" C. (in
Determination
cs-117 I
Slit
of Cl~-CII Naphthalenes
Concn.
8 . 8 5 ~0.112 I 0.028~ 0.027
2,4,5-trimethyl benzoate
benzyI-2,5dimethyl benzoate 2,4-Dimethylbenzyl-2,4dimethyl benzoate
,1
0-100 & I 112.23~ 0.218 10.042
2 2,4-Dimethyl-
3
-1-1
~
0-1001 A1
CisH2002
1 ~
, I
Naphthalene
HASTINOS, Humble
1-Methylnaphthalene 2-Methylnaphthalene 1,2,3,4-Tetrahydronaphthalene
oil 8 Rennins
1 1
Slif
Range
Accuracy
%
%
X or v
0.100
--CllHlo 0-100 h0.5
0.301
1 0.100
16.00p 0.214
1 0.100
I
I
CllHlo
--- I CloHlz
0-100 f0.5 I
Cell Windows: CsBr Absorbance Measuremenf:
Inverse matrix-Graphical-
Successive a p p r o x . 2 -
1 2 3 Material Purify:
298
0
8.85~ 0.398 0.127 0.220 9 8 % minimum
ANALYTICAL CHEMISTRY
Base line-
Inverse matrixGraphical-
P o i n t X Successive o p p r o x - L
Relafive Absorbances-Analyfical Matrix:
Relafive Absorbances-Analyfical Matrix: Componenf/X
Calculafion:
Concn. glliter lengfh mrn
0.389 1
Cell Windows: NaCl Absorbance Measuremenf: Calculation:
Av
0-100 h0.5
lnsfrumenf: Perkin-Elmer M o d e l 1 12, CsBr prism Sample Phase: Solution in carbon tetrachloride
P o i n t X
(mm) AX or
8.1. Pfs.
Jnsfrurnenf: Perkin-Elmer Model 21, NaCl prism Sample Phase: Solution in carbon disulflde
Base line-
C0.n
CS-118
CloHs
0.027
12.99~~0.255 1 10.048~ 0.027
CRYSTALLOGRAPHIC data for publication in this section should be sent to W. C. McCrone, 501 East 32nd St., Chicago 16, Ill.
E* NICHOLSoN and 5. Baytown, Tex.
Component Formula Name
-1-1-
LITERATURE CITED
OPTICALPROPERTIES Refractive Indices. 01, p, and y > 2.20. Surface Character. Continuous spectra in visible light, due to grating effect of twin lamellae.
Determination of Polymethylbenzyl Benzoates
-
Crystals n-ere obtained from A A. Giardini, of this laboratory (melt technique), and from P. G. Cotter, U.S. Bureau of Mines, Norris, Tenn. (aluminotherniic method). R. Lefker, of this laboratory, programmed the machine computations of d-spacings. G. Katz and L. Toman, also of this laboratory, assisted in some of the physical determinations.
*
CRYSTAL ~IORPHOLOGY Crystal System and Class. Orthorhombic, pseudotetragonal; orthorhombic bipyramidal class. Form and Habit. Pseudotetragonal bipyramids, rarely octagonal prisms with bipyramidal terminations; forms observed are orthorhombic bipyramid { 112 1, orthorhombic prism ( 110] , brachydomes { 011 1 and (021) , macrodomes { 101] and { 201 ]. brachypinacoid
0-100 &I
ACKNOWLEDGMENT
12.23~ 0.012 0.154 0.080
12.99~ 0.021 0.047 0.185
Componenflk 1 2
3 4 Material Purify:
20.98~ 16.150 0.251 6.908 0.101 99.5% minimum
18.68~ 0.072 3.507 0.015 0.046
16.00~ 0.302 0.115 1.111 0.048
23.02~ 0.030 0.377 0.042 1.459
