The crystal structure of d-tartaric acid published recently by Beevers and Stern makes possible an absolute determination of the structural configuration of the d-tartaric acid molecule. This is all the more important, as an assignment of absolute configuration to a molecule related to tartaric acid and therefore to a whole class of optically active molecules on the basis of a physical theory of optical activity, seems to be open to criticism

Waser, Jürg

Caltech Authors - Main

The Absolute Configuration of d‐Tartaric Acid
Jürg Waser 
 
Citation: The Journal of Chemical Physics 17, 498 (1949); doi: 10.1063/1.1747297 
View online: http://dx.doi.org/10.1063/1.1747297 
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/17/5?ver=pdfcov 
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498 LETTERS TO THE EDITOR 
'00 
RANGE -2800 mg/ .... (E-504 MEVI 
5000 ~/ ·S400~1 ~ I I 
\ ! 300~1 1 1 
\ .. 20000 Q2 M 015 oa LO FRACTION OF RANGE 
'0 0 FEATHER ANALYSIS 
J\ 
0 1-RA'lS-, 1\"-
1\ 
'0 
\ 
, 500 000 '500 2000 2500 3000 3500 
ALUMNUM ABSORBER ,",g/em' ) 
FIG. 2. Beta-absorption curve. 
LaF 3 twice. Then after allowing 1.5 minutes for more Y94 to 
grow in from its 2-min. Sr parent, yttrium was isolated from 
the solution. 
From eleven beta-decay curves (Fig. 1) and four gamma-
decay curves the average value of the half-life was determined 
as 16.s±1.0 minutes. The decay curves showed two major 
components: 16.s-min. Yand 1O-hr. Y. In most cases a very 
small amount of an intermediate component appeared also, 
probably 3.s-hr. Y. The latter introduced some uncertainty 
into the resolution of the decay curves. By irradiating for no 
more than 10 minutes and by doing the analyses within a few 
minutes after the irradiations, the amount of 3.s-hr. Y which 
grew from its 2.7-hr. Sr parent was kept very low. However, 
it could not be eliminated entirely. The decay curves published 
by Hahn and Strassmann! show the 3.s-hr. component in 
considerably higher relative intensity. This may be an indi-
cation of rare earth contamination since a 3.7-hr. La is known. 
The greater value of 20 minutes they report for the half-life 
of Y94 may have been caused by contamination with 19-min. 
La and other rare earth isotopes. 
The ')'-ray intensity seemed to decay with a slightly shorter 
half-life (15.5 min.) than the {3-ray intensity (16.7 min.) 
10 0 
o'\. 
~ 
& 
0 \., 
0 
0 1'\ 
'\. 
0 
Ti -13.1 """~-z...--' 
'''' 
4 
E-1.4 MEV 1'\ 0 
'\ 
0 ~ .~ iii .. 2 
~ 
'00 10 '520253036 
Pb ABSORBER (Glom', 
FIG. 3. Gamma-absorption curve. 
Although the difference was within experimental error, the 
possibility of the existence of two Y isotopes with similar 
half-lives and radiations was considered. This appears im-
probable because the half-lives obtained were the same 
whether the samples were isolated directly from fission recoils 
or from the strontium parent(s). The assumption of two Y 
isotopes would imply that their half-lives are almost identical 
and/or that both have strontium parents of approximately 
equal half-lives. Either situation is unlikely. 
The beta:- and gamma-radiations were investigated by 
following the decay of several samples through a series of AI 
and Pb absorbers using a mica window (3 mg/cm2) Geiger-
Mueller counter. From the resolved decay curves the absorp-
tion curves shown in Figs. 2 and 3 were constructed. The 
Feather analysis of the aluminum absorption curve indicates 
a range for the beta-rays of 2800 mg AI/cm2, corresponding 
to a maximum energy of 5.4 Mev. The half-thickness in lead 
for the gamma-rays is 13.1 g/cm2, corresponding to an energy 
of 1.4 Mev. The Y samples used for the ')'-ray absorption 
curve were isolated directly from an irradiated uranyl nitrate 
solution. Standard rare earth separations were used only in 
this case. It was found that six potassium rare earth double 
sulfate precipitations were needed in order to remove rare 
earths sufficiently. Praseodymium and neodymium carriers 
were added as well as lanthanum. 
* This document is based on work performed at Los Alamos Scientific 
Laboratory of the University of California under Government Contract 
W-7405-eng-36. 
** Now at Brookhaven National Laboratory, Upton, Long Island, New 
York. 
10. Hahn and F. Strassmann, Zeits. f. Physik 121, 729 (1943). 
2 Katcoff, Miskel, and Stanley, Report LA-659 (Feb. 1948). 
The Absolute Configuration of d-Tartaric Acid 
JURG WASER 
The Rice Institute, Houston, Texas 
March 11, 1949 
I T is well known that the usual x-ray data alone do not permit a distinction between the two possible enantio-
morphic structures of an optically active crystal. I t seems to 
have escaped general notice, however, that in favorable cases 
such an assignment may be made if the face development of 
the crystal is taken into consideration. 
The crystal structure of d-tartaric acid published recently 
by Beevers and Stern! makes possible an absolute determina-
tion of the structural configuration of the d-tartaric acid 
molecule. This is all the more important, as an ~ssignment of 
absolute configuration to a molecule related to tartaric acid 
and therefore to a whole class of optically active molecules on 
the basis of a physical theory of optical activity,2 seems to be 
open to criticism.3 
Figure 1 represents a projection onto the (100) plane of the 
structure of d-tartaric acid as determined by Beevers and 
Stern.! The a axis is oriented towards the reader, the b axis to 
the right, and the c axis up (although the possibility is left 
open by Beevers and Sternl that the b axis might point to the 
left). The van der Waals radii of carbon and oxygen were 
chosen to be 1.4A and L6A, respectively, and the hydrogen 
atoms were omitted. The molecules drawn with. heavy lines 
lie above the others to which they are related by twofold 
screw axes in the b direction. A molecule in the upper left 
shows in detail the relationship between the carbons and 
oxygens except for one concealed carboxyl oxygen. Figure 2 
shows the habits of the monoclinic hemihedral crystals of 
dextro-rotatory (d+) and of levo-rotatory (l-) tartaric acid. 
The monoclinic angle between the faces (100) and (001) is 
100° 17' in either crystal. The orientation of the b axis is the 
same in the two figures. 
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LETTERS TO THE EDITOR 499 
The important distinguishing feature is seen to be the 
appearance of the right sphenoid (011) (faces (011) and (011» 
on dextro-rotatory tartaric acid and of the corresponding left 
sphenoid on levo-rotatory tartaric acid. It is apparent that 
the structure of Fig. 1 corresponds to the face development 
of the dextro-rotatory tartaric acid crystal. A molecular 
arrangement as drawn would tend to develop the faces (011) 
and (011) whose traces are shown in Fig. 1. The rate of growth 
perpendicular to these faces would be low, due to the unfavor-
able orientation of the molecules. For instance, a molecule 
approaching from the right a completed layer bound!!d by the 
plane (011) (Fig. 1) would have to be oriented properly within 
a narrow margin to be able to form the one or two hydrogen 
bonds that will hold it in position. Furthermore, only this one, 
or these two, hydrogen bonds will keep the molecule from 
breaking loose again before further supporting molecules have 
been captured in its neighborhood by the surface. The re-
sulting low rate of crystal growth normal to (011) will cause 
the face (011) to develop very prominently. The non-appear-
ance of the faces (011) and (OIl) is, on the other hand, due 
to rapid crystal growth normal to the corresponding planes. 
Let, for instance, a crystal be bounded by the layer of mole-
cules to the right of the trace of (011) in Fig. 1 (this trace 
O-c 
0-0 
FIG. 1. 
c 
1 
/-
TARTARIC ACID 
FIG. 2. 
would thus actually correspond to the face (On». A molecule 
approaching from the left would eventually be bonded to the 
surface by three or four hydrogen bonds and would be captured 
and swing into position from a much wider range or orientation 
than was the case for the (011) face. The face (110), can also 
be visualized in Fig. 1. It intersects the figure plane parallel 
to the c axis, for instance along the left-hand margin of the 
figure, and slants down from the right to the left. 
The absolute configuration of dextro-rotatory tartaric acid 
is therefore that given by the molecule in the upper left 
corner of Fig. 1 or, if represented by the projection formula,4 
lCOOH 
I 
H-'C-OH 
I 
HO_3C-H 
I 
4COOH, 
by the prOVISIOn that the hydroxyl groups and methylene 
hydrogens are to lie below the plane containing carbon atoms 
2 and 3 and the carboxyl groups to lie above that plane. 
This is just the opposite configuration from the one assigned 
by E. Fischer4 on a postulatory basis. 
A determination of absolute configuration on the basis of 
the pyroelectric effect5 would involve an assumption about 
the charge distribution in the molecule and require a knowl-
edge of the position of the hydrogen atoms. 
1 C. A. Beevers and F. Stern. Nature 162. 854 (1948). 
• W. Kuhn. Zeits. f. physik. Chemie B31. 23 (1936); Naturwiss. 26. 289 
(1938); J. G. Kirkwood. J. Chem. Phys. 5. 479 (1937); 7. 139 (1939); 
Gorin, Walter. and Eyring. J. Chem. Phys. 6. 824 (1938). 
• E. Hiickel. Zeits. f. Elektrochemie 50. 13 (1944); W. Kuhn and R. 
Rometsch. Helv. Chim. acta 27. 1346 (1944). p. 1363; R. Rometsch and 
W. Kuhn. ibid. 29. 1483 (1946). 
• See e.g .. K. Freudenberg, Stereochemie (Leipzig und Wien. 1933), p. 
662ff. 
• See e.g .. P. Groth. Physikalische Krystallographie (Leipzig, 1895), p, 353, 
Thermodynamic Functions of CHaSH and (CHahS 
JOHN L. BINDER 
Akron, Ohio 
March 9. 1949 
SOME time ago the writer had occasion to compute the thermodynamic functions of methyl mercaptan and 
dimethyl sulfide for use in equilibrium studies. In view of the 
present interest in sulfur compounds it seemed desirable to 
present the results of these calculations in an abbreviated 
form now for the use of others. A more complete discussion of 
the calculations will be published later. 
The entropies, free energies, heat capacities, and heat 
contents were calculated for several temperatures by the 
usual statistical methods. The hindered rotation potentials, 
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17 Oct 2016 21:53:30


The Absolute Configuration of d-Tartaric Acid

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The Absolute Configuration of d-Tartaric Acid

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