182

for one of the compounds. Compounds 3, 6, and 7
were studied previously, but have been restudied in
order to obtain more complete and accurate data.

The numbers used to designate these correspond with
those used in the previous report. Numbers 8 through
13 are additional compounds. Except as indicated
below, the wavelengths which could be studied are in

- the first absorption band of the compound.
Some experimental details are as follows:

short-wavelength end of the first absorption band.
Two possible explanations suggest themselves, either

or both of which could be involved in a given instance. (a) Broadly speaking, the shorter the wavelength absorbed, the higher the vibrational state to
which the molecule is raised and the greater the excitation energy involved in the instantaneous (10~”

second) vibrational-relaxation process which follows.

To

If the molecules having had the greater excitation
energy now end up with greater rotational energy,
which they retain during the period preceding emission, then greater depolarization would be observed

mu. In all cases signals were sufficiently large to permit use of such narrowslits. No set rule was followed
concerning the number of times a measurement was
to be repeated; however, enough repetition was carried out to make a result convincing, especially where

tween the first. and second absorption bands, and if
the second band is of the opposite type (as regards
90° shift or no shift) the two opposite polarizations

achieve maximum spectral purity, monochromator
slits were kept very narrow, 0.9 and 0.6 mm,
respectively, for entrance and exit slits; this corresponds to a half-intensity band width of only 1.6

it seemed crucial. In general, because of the great varlations in absorbance of a solution at the different
wavelengths, more than one concentration of solution

was needed in covering each spectrum.

In the first report, mention was made that (for the

for them. (b) There may be a region of overlap be-

will tend to cancel each other. For compound 13 (see

also Figure 139), it was possible to extend the measurements into the second absorption band, and explanation (b) seems to be confirmed, although (a)

may be involved as well. Second, hidden transitions

seem likely or possible in two of the compounds-—

in compound 6 at about 330 my and in compound 7 at

particular geometry of our apparatus) calculations
showed that maximum signal would result when the
absorbance is 0.9. However, it was found that solu-

about 320 mp.
It might be added at this point that both positive
and negative polarizations were observed, that the
most positive and most negative values (+45 and

antly omitted from the polarimeter diagram of the
first report) which sends the incident beam back
through the cell. Evidently this is more effective
than was assumed.
A test was performed to learn something of the
magnitude of the signal, produced by incident light

theoretical limits (+50 and —33144%, respectively),
and that, therefore, the observations attest to the
reliability of the apparatus.

tions somewhat more dilute than this gave stronger
signals. In the cell chamber is a reflector (inadvert-

scattered in the cell, reaching the photomultiplier

after attenuation by the appropriate fluorescent-beam
filter. The polarimeter was operated with the solvent

alone in the cell (fluorescent solute missing} and signals recorded for each filter used at each incidentlight wavelength used. Because of xenon-source instability, mentioned in the first report, readings taken

at different times have been found to vary consider-

ably; however, if the values obtained in this test
were to be used as signal corrections, the effect on P
(expressed as percent) would be to change it (negatively) by only 0.1 in 70% of the instances and by no
more than 1 in any instance. Considering this and

other possibilities for error, the total uncertainty in
P is perhaps no greater than 2 [that is, P = 41%
means P = (41 + 2)%, etc].

Certain features of the results in Table 66 are of

particular interest. First, in every instance, the polar-

ization drops as one moves from the long- toward the

—19%, respectively) were reasonably close to the

INTRINSIC VISCOSITY STUDIES

Tests in which depolarizations of the three binaphthy] derivatives are compared are continuing, but
as yet, because of our inability to secure sufficiently

precise and reproducible results, no conclusion has

been reached as to whether there are or are not differences among them. Tentatively, one might conclude that if there are effects, they are of small mag-

nitude. Temperature control is no longer a major

problem; other factors appear to interfere and need

to be investigated. A slight change in the position of

the cell or in the level of the liquid in it may affect

the results enough to obscure the effect. Also, certain

observations have suggested that the compounds used

may undergo a photochemical reaction when exposed
to the UV radiation.
'REFERENCES

1. Anderson, W. R., Berlman, I. B., and Wirth, H. O. Argonne
National Laboratory Radiological Physics Division Annual Report, July 1966-June 1967. ANL 7360, pp. 1-4.
2. Platt, J. R. J. Chem. Phys. 17, 484-495 (1949).

Select target paragraph3