THE VISIBLE ABSORPTION SPECTRUM OF BROMINE

IN SOLUTION

By N. S. BAYLISS,"A. R. H. COLE,*and B. G. GREEN*

[,Warmscript received August 12, 19481

Summary
The visible absorption spectrum of bromine was measured in n-hexane (a normal
solvent) and in concentrated sulphuric acid (at room temperature and a t -70° C.),
phosphoric acid, and ethanol (at -70' C.) as associated solvents. The absorption
continuum a t 4150 A. in the gas is displaced slightly to the red in n-hexane although
other normal solvents may displace it to the violet. The displacement to the violet is
greater in associated solvents, ranging from 650 em.-l in sulphuric acid to over 2000 em.-1
i n ethanol. The displacement in sulphuric acid glass a t -70' C, is nearly double the
value a t 18' C. The displacements in associated solveilts are explained in terms of
the effect of the semi-rigid cage of solvent molecules surrounding each bromine molecule,
and the assumption of " solvates " is unnecessary and undesirable. The spectra in
solution are between 40 and 70 per cent. more intense than in the gas, about double
the increase that would be predicted by Chako's treatment of the effect of Lorentz-
Lorenz forces. The differences in the shape and Emax between solutions in sulphuric
acid a t 18' C. and a t -70' C. are due to the different statistical distribution of bromine
molecules between the vibrational energy levels.

I n spite of the satisfactory state of the theory of the absorption spectra of

diatomic gases, the changes in the position and intensity of the absorption bands
of even simple molecules under the influence of solvents are still far from complete
interpretation. The work presented in this paper is in continuation of a pro-
gramme(1) to use simple molecules such as bromine, whose gaseous absorption
spectrum is reasonably well understood, as the experimental material in an
attempt to isolate the factors that are responsible for solvent effects on spectra.
Previous investigators of the absorption spectrum of bromine in solution
include the following : Bovis(2), Gillam and Morton(3), Child and Walker(4),
Aickin, Bayliss, and Rees(l), and Prikhotko(5). Although they are not in
perfect agreement, some general conclusions may be drawn from their results.
The absorption continuum responsible for the visible colour of bromine gas
(~,,=152 at 4150 A.) is increased somewhat in intensity in solution, and the
position of the maximum is displaced slightly, usually towards higher frequencies.
I n " normal " or non-associated solvents the displacement is of the order of a
few hundred om.-I ; in associated solvents it is rather greater-of the order of
1000 em.-1 to higher frequencies. At low temperatures the displacement appears

* Department of Chemistry, University of Western Australia.

 VISIBLE ABSORPTION SPECTRUM O F BROMINE 473

to be greater, amounting to 1300 em.-l in pentane at liquid hydrogen

temperatures(5).
This paper describes measurements on the visible absorption spectrum of
bromine in n-hexane as a typical normal solvent, and in ethanol, concentrated
sulphuric acid, and concentrated phosphoric acid as associated solvents, Meaeure-
ments in sulphuric acid are described at -70" C. as well as at room temperature
in order to study the effect of freezing the solvent to a rigid glass. The measure-
ments in ethanol were carried out at -70" 0. in order to avoid the reaction
between bromine and alcohol which is appreciable at room temperature.

11. ~/IATERIALS
Bromine.-A B.D.H. " Analar " sample was used which contained less than
0.0005 per cent. of iodine according to the Analar tests.
rz-Hexane.-A B.D.H. sample was washed repeatedly with concentrated
sulphuric acid and distilled. We could not remove a trace of benzene which
could be detected by its absorption spectrum at 2600 A.
Ethanol.-Benzene was rembved from a commercial sample of absolute
alcohol by adding some water and fractionating. The purified sample was
completely transparent to 2200 A.
fiulphuric acid.-B.D.H. L L nitrogen-free " sulphuric acid (98 per cent.)
was diluted with water to 90 per cent. This procedure was found necessary to
void crystallization and t o promote the formation of a glass when the acid was
cooled to -70" 0.
Phosphoric acid.-The B.D.H. sample of orthophosphoric acid (sp. gr. 1.75)
was transparent to 3200 A.

111. EXPERIMENTAL
Measurements at room temperature were carried out by the method of
photographic spectrophotometry described by Aickin, Bayliss, and Rees(1).
For the measurements at -70" C., the solutions were contained in a Hilger
Presil " cell, 4 om. long, mounted in a thermally insulated copper bath con-
taining a mixture of solid carbon dioxide and ethanol. The cell was held tightly
between two re-entrant side tubes with outside silica windows, thus providing
air gaps which protected the cell windows both from the bath liquid and also
from deposition of frost from the atmosphere.
The results are expressed in terms of the molar extinction coefficient E defined
by the usual formula logl,,(Io/I)=sod, where I, and I are respectively the incident
and transmitted intensities, o is the concentration of bromine in mole litre-l,
and d is the length of the absorbing path in cm. The bromine concentration
varied between 0 a0002 and 0.0015 mole litre-l.

IV. DISCUSSION
The results are shown graphically as absorption curves in Figure 1, and are
summarized in Table 1,which for comparison includes data obtained b y Aickin,
Bayliss, and Rees(1) in other solvents. The absorption continuum under
474 N. S. BAYLISS, A. R. H. COLE, AND B. G. GREEN

consideration is known to consist of two components, A (A, in gas=4150 A.)

and B ,A( in gas =4950 A.), which have been identified with the electronic
transitions-A : lII,tlC,+ ; B : ~II,+,tlCg+, 311,,tlCg+ (Acton, Aickin,
and Bayliss,6 ; Bayliss and Rees,7 ; Rees,8 ; however, see Mulliken,9).
The data in Table 1refer to the stronger A component, and include the displace-
ment (Av,,,) of the absorption maximum in each solvent, and also the intensity
of the continuum expressed in terms of the oscillator strength f as defined by
the relation(l0)
f =4 a 3 1 x 10-9J'y~dv
..
~ 4 . 3 1 ~ 1 0 - ~ y ~ .~. .~. ., .A. .v. .~. . . . . . (1)
The factor y contains the refractive index of the solvent ; but in view of the
uncertainty about its true value it is taken as unity for the time being in
accordance with the suggestion of Mulliken and Rieke(l0). The half-width of

WAVELENGTH I A I

5000 4500 4000

WAVE NUMBER (cM.")

Fig, 1.-Visible absorption spectrum of bromine solutions showing molar

extinction coefficient E plotted against wave number. The maxima are
numbered as follows : 1, Br, gas ; 2, in n-hexane ; 3, in sulphuric acid a t 18' C. ;
4, in sulphuric acid a t -70' C. ; 5, in phosphoric acid ; 6, in ethanol a t -70' C.

the continuum, Av,, is the separation in em.-l between the points where E =BE,,.
Owing to the contribution made by the B component on the low frequency side
of the A maximum, we have assumed for the purpose of calculating Av+ that
the A component is symmetrical about v,, and Avt has been taken as twice the
separation between v, and the point on the high frequency side where E
From Figure 1and Table 1,the solvent effect is seen to consist in a displace-
ment of the A maximum ranging from -100 em.-l (m-hexane) to 500 em.-1
(carbon tetrachloride) in the normal or non-associated solvents, and from
650 om.-I (sulphuric acid) to 1400 em.-l (water) in the associated solvents.
,Cooling sulphuric acid to a glass a t -70" C. nearly doubles the displacement.
The inorease in, the intensity f varies from 40 per cent. in %-hexme to nearly
 VISIBLE ABSORPTION SPECTRUM O F B R O Y I N E 475

70 per cent. in sulphuric acid. The displacement and the intensity of the A
component in ethanol are almost impossible to estimate with any accuracy
owing to the proximity of a very strong absorption band in the ultraviolet.
Our results in ethanol are at variance with those of Child and Walker(4) in that
we obtain a considerably greater value for the apparent ,c,, at 3740 A. and a
much shallower minimum in the absorption curve before the onset of the strong
ultraviolet absorption band. We believe the discrepancy to be due to the
behaviour of the ultraviolet band, which is under investigation and will be
discussed in a future paper.

( a ) T h e Effect of 8olvents o n v,,,

The smaller displacement of v,,, in non-associated solvents has been
attributed to the operation of van der Waals' forces, and the larger displacement
in associated solvents to the formation of solvates(4). The case has been regarded
as analogous to the distinction between the " red " and L'brown " solutions of
iodine in non-associated and associated solvents respectively, where solvation
has also been invoked to explain the greater displacement of the absorption in
the brown solutions(l1, 12). I n both bromine and iodine the absorption band is
displaced between about 1000 and 2000 em.-l to higher frequencies ; but in
bromine the change in colour is not so obvious since the undisplaced band is
already further to the violet. Solutions of bromine in ethanol at -70" 0. are
pale yellow in colour, however (see the absorption curve in Fig. 1).
There are many arguments against solvation in these solutions, at least
in so far as the spectroscopic evidence is concerned. I n the first place, " solva-
tion " is an ill-defined term ; but if any real solvation in the chemical sense is
meant, it must imply the formation of bonds that are strong compared'with kl',
say at least as strong as a hydrogen bond. If there is solvation of this kind in
solutions of bromine in associated solvents, it is remarkable that there is so little
difference between the spectra in associated and non-associated solvents, or
between the former and the gas, in respect both of position and intensity. I t is
also difficult to understand why solvates in different associated solvents should
have such similar spectra. I f solvates are responsible for the displacement of
650 em.-I in sulphuric acid at room temperature, it is difficult to account for
the further displacement of 500 om.-I when the acid is frozen to a glass or for the
displacement of 1300 em.-l in pentane a t low temperatures(5). If there is any
kind of chemical equilibrium between solvated and unsolvated bromine molecules,
one would expect that changes in concentration would cause opposite changes in
the intensities of the band due to unsolvated molecules and that due to solvates
with a constant value of E a t the point where the absorption curves cross. There
is no evidence of this behaviour in the spectra of solutions of either bromine or
iodine.
Consideration of the data in Table 1reveals a regular trend in the values of
E~,,, Av,,, and Avt. With the exception of irregularities in cyclohexane and
cmbon tetrachloride, and in sulphuric acid at -70" 0. which is discussed later,
the half-width Avt increases regularly as Av,,, increases. There is also a
parallel decrease in E,, although in this case the non-associated and the
476 N. S. BAYLISS, A. R. H. COLE, AND B. G. GREEN

associated solvents must be regarded as two separate groups. This regularity

of behaviour is more likely to result from the operation of some (probably
imperfectly understood) physical factor than from a chemical solvation which
would seem to imply some individuality in solvents of differing composition.
TABLE1
DATA RELATING T O A MAXIMUM O F BROMINE I N SOLVENTS

Dis-
Temper. place- 1 Half- Oscil-
Solvent ature ment width lator
(" c.1 a Av* Strength
(em.-1) 1 (om.-1) (f)
I

(Gas) (a) . . .. ..
12-Hexane . . .. ..
Cyclohexane (b) . . ..
Chloroform (b) .. ..
Carbon tetrachloride (b) . .
Sulphuric acid .. ..
Sulphuric acid .. ..
Phosphoric acid .. ..
Water (b) . . .. ..
Ethanol .. .. ..
(a) Data from Acton, Aickin, and Bayliss(6).
(b) ~ a t from
a Aickin, Bayliss, and Rees(1).
Bayliss and Rees(l3) have shown that the assumption of solvates in the
chemical sense is unnecessary, and that the spectra of bromine and iodine
solutions can be explained in terms of the cage of solvent molecules that encloses
each solute molecule. Without assuming any special solvation forces but
merely those physical forces that are responsible, for example, for the activation
energy of diffusion, the presence of the cage introduces a potential energy barrier
(of the order of magnitude of the activation energy of diffusion) which modifies
the U ( r )curves of both the normal and excited states concerned in the electronic
transition. The corresponding wave functions are modified, and the application
of the theory of continuous absorption spectra(l4,15)made it possible to account
qualitatively for the displacements and the changes in symmetry of the absorption
curves of bromine and iodine in non-associated solvents.
In associated solvents, the hydrogen bonding that is responsible for associa-
tion leads to a certain preferred "hole " size in the solvent which is usually
smaller than solute molecules such as bromine and iodine. In these cases,
there must be mutual accommodation between solvent and solute which rewilts
in an expansion of the solvent '' hole " and a slight compression of the solute
moleoule in its ground state. This slight compression is sufficient to account
for the greater displacement of the absorption band since the Franck-Condon
transition from the ground state is to a point of higher energy in the excited
 VISIBLE ABSORPTION SPECTRUM O F BROMINE 477

state. Rees(l6) has since obtained a quantitative evaluation of the work needed
to expand the solvent cage in terms of the surface tension of the solvent, and has
calculated displacements of the bands of iodine and bromine in water (1300 em.-l
and 1400 om.-l respectively) that are in good agreement with the experimental
values (1800 em.-l and 1400 em.-l*).
The above interpretation of the effect of associated solvents leads to the
quditative predictions that the displacement of ,v, should be less in associated
solvents of greater natural hole size, end also that increasing the rigidity of
the solvent (as in freezing) should increase the displacement. The latter effect
is obvious in the absorption curves in sulphuric acid at room temperature and at
-70" C. (Fig. 1). It can be shown that the former effect is realized in solutions
in sulphuric and phosphoric acids as compared with water, although the data
on these solvents are not sufficient to carry out a quantitative calculation.
The normal hole size in water is about 3.4 A. in diameter(l7), which must
be expanded to accommodate a bromine molecule of diameter about 5 A. Con-
centrated sulphuric and phosphoric acids have been shown by X-ray methods(l8)
to contain tetrahedral SO4-- and PO,--- ions associated by hydrogen bonds.
The distance between the hydrogen bonded 0 atoms is 2.85 A. and the angle
between the H - 0 and the 8-0 or P-0 bonds is given as tetrahedral. Using
Pauling's(l9) values of 1.51 A. and 1.55 A. for the 8-0 and P-0 distances
respectively in the ions, it can be deduced that the closest approach of two 8
nuclei in sulphuric acid is 3.86 A., and of two P nuclei in phosphoric acid is
3 90 A. These values lead to effective packing radii of 1 93 A. and 1.95 A.
for the SO4-- and PO,--- ions respectively. The effective packing radius of
the H,O molecule in water is 1.38 A.(17). Eence one concludes that the normal
hole size in the two acids is considerably greater than in water. Their surface
tensions (63 dyne em.-l for 90 per cent. sulphuric acid) are not very different
from that of water (73 dyne em.-l). It is therefore to be expected that the
compression of the bromine molecule will be less in the acid solvents than in
water, and consequently the displacement of the absorption maximum will
also be less, as observed.

( b ) T h e Effect of L3olvents o n the Intensity

Dealing first with the pwticular case of the solutions in sulphuric acid, it is
to be noted that although ,E, is increased from 212 to 238 on going from room
temperature to -70" C., the total intensity of the band as measured by its
oscillator strength f is the same a t the two temperatures. Acton, Aickin, and
Bayliss(6) have shown that the absorption spectrum of bromine gas is the sum of
contributions from molecules distributed in statistical equilibrium between the
various vibrational states v" =0, v" =l etc. These contributions obey a sum rule
so that the total intensity of the electronic transition is independent of temper-
ature, even though the value of,,,s and the breadth of the band may change.

* Rees quotes 1760 om.-l for this displacement from Aickin, Bayliss, and Rees(1). A re.
examination of the data of these authors gives 1400 em.-1 as a better value.
478 N. S. BAYLISS, A. R. H. COLE, AND B. G. GREEN

At low temperatures, the contribution from the state u"=O becomes more
important, resulting in greater ,E, a narrower absorption band, and a more
pronounced hump on the low frequency side due to the B component of the
absorption (cf. absorption curve of the state v"=O, Acton, Aickin, and Bayliss,6).
These features are evident in the comparison of the absorption curves in Figure 1
for sulphuric acid a t the two temperatures.
A statistical calculation at -70' 0.shows that practically all the molecules
in bromine would be in the vibrational states vU=O (89.6 per cent.) and v" =l
(10.4 per cent.). Using the extinction coefficients determined by Acton, Aickin,
and Bayliss(6) for these states, it is calculated that ,E,, in bromine gas at -70' 0.
would be increased 10 per cent. over its value at room temperature. Table 1
shows that in sulphuric acid, ,E,, is increased 12 per cent. at -70" C. I t is
clear from these results and from the constant value o f f that the temperature
effect in sulphuric acid solution is explained by changes in the statistical distribu-
tion of bromine molecules between their various vibrational states, whatever
may be the reason for the overall increase in intensity of nearly 70 per cent. as
compared with the gas.
Chako(2O)has considered the relationship between the f values of absorption
bands in the gas state and in solution on the basis of classical dispersion theory,
and in terms of the clarification of his work by Mulliken and Rieke(l0) has shown
that the existence of the Lorentz-Lorenz forces in solution requires the factor y
in equation (1) to haye the value 9 % / ( ~ ? + 2 )if~ , m is the refractive index of the
solvent. The solvents in Table 1 have refractive indices lying roughly between
1 4 and 1.5 ; y is therefore between 0 8 and 0.75, and the resulting values of f
are between 0.8 and 0.75 of the values quoted in Table 1. Chako's theory is
thus able to account for about half of the observed difference in intensity between
absorption in the gas state and in solution. The remainder of the difference
cannot be explained precisely in view of the present state of the theory of absorp-
tion spectra in solution. It may be due to the inaccuracy of the classical
dispersion theory used by Chako, or else to solvent perturbations modifying the
selection rules of the weak or forbidden transitions that are responsible for the
spectrum (10).

V. ACKNOWLEDGMENTS
We wish to acknowledge support from the Commonwealth Research Grant
to Australian Universities in the form of a studentship (A.R.H.C.) and from the
Hackett Fund of the University of Western Australia in the form of a research
scholarship (B.G.G.).

VI. REFERENCES
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(2) Bovrs, P.-Ann. Phys. Paris 10 : 232 (1928).
(3) GILLAX,A. E., and MORTON, R. A.-Proc. Roy Soc. A 1 2 4 : 604 (1929).
 V I S I B L E ABSORPTION SPECTRUM O F B R O N I N E

(4) CHILD, C. L., and WALKER, 0. J.-Trans. Faraday Soc. 34 : 1506 (1938).
(5) PRIKROTKO,8.-Acta Physicoohim. U.R.S.S. 16 : 125 (1942).
(6) ACTON,A. P., AICKIN, R . G., and BAYLISS,N. 8 . 4 . Chem. Phys. 4 : 474 (1936).
(7) BAYLISS, N. S., and REES, A. L. G.-Ibid. 7 : 854 (1939).
(8) REES, A. L. G.-Proc. Phys. Soc. 59 : 1008 (1947).
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MULLIKEN,R . S., and RIEEE, C. A.-Rep. Progr. Phys. 8 : 231 (1941).
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FAIRBROTHER, I?.-~Vature, 160 : 87 (1947).
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GIBSON, G. E., RICE, 0. K., and BAYLISS,N. 8.-Phys. Rev. 44 : 193 (1933).
BAYLISS,N. S.-PTOC. Roy. Soo. A 1 5 8 : 551 (1937).
REES, A. L. G.-J. Chem. Phys. 8 : 429 (1940).
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FINBAK, C., RBNNING,O., and VIERVOLL,H.-Tidsskr. Kjemi Bergv. iMet. 4 : 26 (1944).
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PAULING,L.--" The Nature of the Chemical Bond." (Cornell Univ. Press : Cornell, 1940.)
CHAKO,N. Q.-J. Chem. Phys. 2 : 644 (1934).