Solvent effect on the charge transfer intfm3ity of benzene-iodine

complex*
B. B. BHO~MIK
Department of Physical Chemistry, Jadavpur University, Celautte, India

(Received0 October1060)

Ah&a&-The chargetransferintensity of the benzene-iodine complex is determinedin different

solvents such 8s cyclohexane, methylcycIohexane, n-heptane, carbon tetrachloride and 1,2-
dichloroethane. The results show that with the oh8uge of solvent, the ob8rge transfer intensity
of the oomplex is also oh8nged. The thermodynamic properties of the benzene-iodine complex
in different solvents 8re also different. The important role of solvent for the change of thermo-
dymunio 8s well 8s spectrophotometriapropertiesof benzene-iodine oomplex is suggestedto be
due to the inters&ion with iodine.
INTRODUCTION
ACCORDINCJ to MULLIKEN[l], the intensity of the charge transfer complexes should
increase with the increase of the stability of the complexes, unless different sets of
orbitals are involved in the two phenomena. This is found true i.e. the oscillator
strength cf) of the charge transfer transition varies directly with the enthalpy change
( -AP) of iodine complexes with N-heterooyolics [2]. But charge transfer complexes
of iodine with benzenes disagree with Mulliken’s prediction. In the oaee of weak
charge transfer complexes, the role of solvents is very important [3-71. The different
values of equilibrium constant of the same benzen+iodine complex in different
solvents such as heptane, carbon tetrachloride and benzene [8] suggest that the role
of solvent interaction with iodine cannot be neglected. On the other hand, a high
equilibrium con&tint of the benzene-iodine complex with low molar extinction
coefficient vslue in the gas phase [9] again supports the solvent effect for this complex.
Whether the intensity of the charge transfer complex of benzen&odine is affected
with the change of solvents, whether the intensity of the complex is related with its
stability in different solvents, it is for this purpose the complex of benzene-iodine is
re-investigated in different solvents. The results are reported in this article.
EXPERIMENTAL
Fisher certified iodine was resublimed under reduced pressure. Speotrograde
benzene was supplied by Eastman Organic Chemicals and was fractionally distilled
just before use. The speotroquslity solvents were supplied by Eastman Organic
* Part of this work was done by the 8uthor St the Department of Biophysics, Michig8n
State University, Eest L8nsing, Michigan, and supported by National Aeronautics and Space
Administretion Grant NSG 476 end Netio& Institutes of Halth Grant G&1422.
[1] R. S. MULLIKE N, J. Am. Chem. Sot. 74, 811 (1962).
[Z] V. G. KRISRXAend B. B. BHO~MIK, ibid. 90,170O (1968).
[3] J. M. CO~UULL, R. FOSTERand D. L. HAXICX, J. Chem. Sot. 1202 (1066).
[4] R. E. MERIUIFIE LD and W. D. Pm~rrs,J. Am. Chem. Sot. 80,277s (1068).
[6] M. T-s, J. Phya. Chem. 65,664 (1961).
[S] S. CAR-, J. N. M-L.L and E. J. ROSCE,J. C?wm. Sot. 2048 (1966).
173 P. J. TRO- and M. W. HANNA, J. Am. C&m. Sot. 88, 3724 (1906).
[S] T. M. CRO~~~~LLand R. L. Scorr, ibid. 72, 3826 (1960).
[O] F. T. LANG 8nd R. L. Srnoxa, i&d. 87, 2346 (1966).
321
322 B. B. BH~WNIK

Chemicals and Matheson Coleman and Bell and these were used without further
purification.
Absorption spectra were recorded on a Cary Model 16 spectrophotometer with
fused silica cells of 1-O cm optical path length.
RESULTS
In Fig. 1 are shown the spectra of mixed solutions with a fixed concentration of
iodine and varying concentrations of benzene in cycclohexanesolvent at 24°C. These
I

Wovelength, mp

Fig. 1. The ultra-violet absorption specks of iodin+benzene solutions. The

spectra were reaorded in cyclohexsne at 24% with I-om cells. Concentration of
iodine: 6.30 x 10-*X Concentration of benzene (M): (1) 0.0, (2) O-1123, (3)
0.2246, (4) 0.3369, (6) 0.4492, and (6) 0+613. The curve (7) represents the spectra
of benzene of concentration O-209 M.

spectrophotometric data were employed to calculate the equilibrium constant for the
benzene-iodine complex in different solvents using the SCOTT modification [lo] of the
BENESI-HILDEBRAND equation [ll]. This equation can be written

~lYI[~l~ =- rm 1
(1)
d % +K,e,
[lo] R. L. SCOTT,Rec. Traw. China. 75, 787 (1960).
[l l] H. A. BENEPI and J. H. HILDEBRAND, J. Am. Chem. Sot. 71,2703 (1949).
 Solvent effeot on the charge transfer intensity of benzene-iodine complex 323

where [A] and [I)] are the initial concentrations of the acceptor and the donor,
respectively; I is the cell length ; d the optical density of the complex, K, the equilib-
rium constant (in l/mole) and a, is the molar extinction coefficient. If [A][DJZ/d is
plotted against [D], a straight line with slope l/g, and with intercept l/&q, should
result for a 1: 1 complex. However, it is a prerequisite for the equation in the present
form that [D] > [A] and that the complex absorbs at a wave length where A and D
are completely transparent. In the present case the small absorption due to iodine in

Table 1. Thermodynamio and spectrophotometriaresults of benzene-iodine oomplex

in different solvents according to Scot modification of Benesi-Hildebrand equation

K, Charge-transferband
(l/mole) -AH’ AP -@ LX %lllIU
Solvent (24%) (kcal) (keel) (e-u.) (mp) x 10-b f
Cyclohexane 0.260 1.72 0.80 8.62 289 1.114 O-271
Methylcyclohexane 0.262 169 0.81 8.46 289 l-169 0.276
n-Heptane 0.246 1.62 0.83 9.26 288 l-200 0.280
Carbon tetrachloride 0.184 1.41 I.00 8.14 291 1.346 o-319
1,2-Dichloroethane 0.116 0.99 1.28 7.66 290 1.294 O-348

cycclohexaneor in any other solvent is considered to calculate the equilibrium constant.

The enthalpy and entropy change of this complex in different solvent were obtained
from the equilibrium constants at three different temperatures (40, 24, 14°C) by the
usual method [12]. The measurements at 40 and 14°C were made by preheating and
precooling the cells with the solutions in a constant-temperature bath. The thermo-
dynamic properties of the benzene-iodine complex in different solvents determined by
equation (1) are shown in Table 1. As reported before [2], the charge transfer band of
the benzene-iodine complex in different solvents was obtained by balancing the
solution of the complex against thl equilibrium concentrations of free donor and free
acceptor present in the solution of the complex.
The oscillator strength was obtained from the approximate formula [13]

f = (4.319 x lo-B)&,,Y,,, (2)

where ~i/z is the band width for half-intensity in cm-l. The spectrophotometric
properties of the benzene-iodine complex are also shown in Table 1.

DISCUSSION
The experimental results (Table 1) of the bermem+iodine complex in different
solvents show that the stability of the complex (-AHO) inoreases with the decrease
of the charge transfer intensity i.e. the oscillator strength of the complex cf). For the
weak charge transfer complexes, the use of Benesi-Hildebrand equation for the
determination of the equilibrium constants and molar extinction ooeffioients is

1121 L. J. kiNDBEWS and R. M. KEEPER, ikfokmdm t.hqhwa in &qanie Ckenvishy, p. 104.

Holden-Day ( 1964).
[13] H. TSWOBXUEA and R. P. LANG,J. Am. Ohem. Sot. 88,208s (1961).
324 B. B. BHOWIUK

criticised by different authors [3-6, 10, 14-201, primarily from the stand points of
thermodynamic non-ideality and of solvent competition with molecular complexing
CARTERet al. [S] have introduced a model consisting of a single equilibrium between
solvated species in which A, D and AD are each assumed to have a well-defined
solvation shell. In deriving their equations Carter et al. have used units of molarity
for all concentrations except that of the solvent which is in mole fraction units.
TROTTER and HANNA [7] have simplified their equations by assuming that D is not
specially solvated and using same units for all concentrations. In molar units this
equation is

(3)

where 9, and V, are molar volumes of solvents and donor, respectively. The equa-
tion (3) is derived for the conditions that [D] I 1 and q 5 3. When q = 0, it is
nothing but the Benesi-Hildebrand equation. On the other hand, when the donor
and the acceptor are both solvated and considering the equilibrium between solvated
components as
AS,, + DS, + ADS,, + qS (9
the equation (3) can be written in the form,

1
CAI[DP 1000 Q 1 q(m + 1)(1000)+1
y=--
d ( v, > a.K,+F Cl--
(5)
( v$)a-1&

where A = V,/ V,. The equation (5) does not differ from the equation deduced by
Carter et aL, if molar concentration of the solvent is considered instead of mole
fraction in the latter case.
Suppose the data which have been analyzed by means of the equation (1)
[Benesi-Hildebrand equation] are used for the equation (6). Then

K,(B -H) = = JL- - q(m+

in;Ezpt 4
(FE-J (7)
and
1 K
&,(I.3- H) = - = XL
slope K$- H) 1000 q
t-19,
It is clear from above relations that a B - H analysis underestimates rZband over-
estimates e,. Using either equation (3) or equation (6) no satisfactory results are

[14] L. E. OBC+ELand R. S. MULLIKEN, J. Am. Chem. Soo. 79,483Q (1967).

[16] N. J. ROSE and R. S. DRAOO,ibid. 81, 6138 (1969).
[I61 N. B. JTJRINSKIand P. A. D. DE MAINE, ibid. 86,3217 (1964).
[17] W. G. BARB, Tram. Faraday Sot. 40, 143 (1963).
[IS] P. R. HAXXOND, J. Chem.Soc. 479 (1964).
[lQ] W. B. -SON, J. Am. Chem. Sot. 87, 167 (1966).
[ZO] G. D. JOBNEON and R. E. BO~EN,ibid. 37,1655 (1966).
 Solvent effect on the charge transfer inteneity of benzene-iodine complex 326

obtained for the bensene-iodine complex in different solvents. As for example, the
values obtained by using equation (3) [when q = l] for the benzene-iodine complex
in cyclohexane are 9, (24%) = 3.23, -AH0 = 1.24 kcal and E, (24’C) = 8275. The
molar extinction ooefficient is not found constant at different temperatures. The
values at different temperatures are 8430, 8275 and 7980 at 14,24 and 40% respec-
tively. On the other hand, a constant value of molar extinction coefficient at different
temperatures leads us to believe that the density of the solvent should increase with
the increase of temperature. Higher values of Q give very high value of equilibrium
constant without giving too low molar extinction coefficient value. Taking different
values of m, this relation is not improved, e.g. when nz = 2, and q = 1, the values
found for the benzene-iodine complex in cycZohexaneare K, (24’C) = 6.24, - AH0 =
O-925kcal and E, = 5100. Again different values of E, are found at different tem-
peratures. Thus using single equilibrium between solvated species in the charge
transfer interaction of benzen+iodine complex in different solvents, it has been
found that the relation between the stability and the intensity of the complex is not
improved from the B - H treatment. Considering second equilibrium between
iodine and the solvent in addition to the normal benzene+iodine interaction, an
equation can be developed. This type of equation has been deduced previously by
different authors [3,4], but in all cases, it is expressed in mole fraction unit. Suppose
the reactions
D+A+DA
[Gl
K1 = Wl{PU - IX41- CGI)
S+A+SA
w
Ks = tSl(t4 - VJ,l - K%
where [C,] and [C’s] are the molar concentrations of iodine complexes of benzene and
the solvent respectively. For the experimental conditions employed, [D] > [C,] and
~&mat~o~J. Then an analysis similar to the derivation of equation (1) yields the

[Al[DP
- = IDI 1 + ~@I
d Jwl + KBWI (8)
” + ” &ID] & % + ‘8 K,[D]
( )
Since iodine in the vapour state haa no absorbance at the region of charge transfer
spectra of iodine with benzene, the little absorbance of iodine in other solvents such
;t8 cyclohexane or n-heptane at this region is taken into account due to the contact
charge transfer complexes [14, 211 of iodine with these solvents. The term s&[S]/
RJD]) appears when absorbance due to the contact charge transfer interaction of
iodine with the solvents is considered. s, is the molar extinction ooeffioient of the
iodine-solvent contact charge transfer complex at that wavelength region. Com-
paring equation (8) with equation (l), one obtains the relation

Kl
Rc= 1 + RJS]
(9)

[Zl] L. M. JIJMENand W. B. l?EfWON, J. Phys. Chme. 73,3069 (1968); additional refmnoea em

cited in this paper.
326 B. B. BEOWXIIE

Table 2. Results for the iodine complexes with different solvents

Visible bend
(E) -AH0 of iodine
Solvent (24%) (kcal) A(mA

Cyclohexane 0.0791 0.87 623

Methylcyclohexsne 0.0978 1.02 623
n-Heptene 0.1216 1.17 622
Carbon tetreohloride 0.1390 1.28 617
I,2-Diohloroethane 0.2290 1.62 497
Benzene 0*4600 2.28 600

* Equil. oonstant mentioned here is free from the intersction of other

solvent.-
2.!

240 280 320

Wavelmgth, rnp
Fig. 2. The charge transfer spectrcrof iodine complex with benzene. The ape&r8
were reoorded in benzene at 24% with I-cm oells. Concentration of iodine:
2.00 x 10-a M.

This equation shows that the K, calculated from equation (1) is function of K,, the
interaction with the solvent. To get correct value of K,, the equilibrium constant
of the benzene-iodine complex free from solvent, the correct value of K,, the equilib-
rium constant of the iodine+solvent i&era&ion free from other solvent is needed.
Unfortunately, no value of equilibrium constant of the iodin-olvent interaction ie
 Solvent effect on the charge transfer intensity of benzene-iodine complex 327

reported free from other solvent. The value of the equilibrium constant of the iodine-
cyclohexane complex is reported in heptane solvent [22, 231. Taking this value from
the latter and also knowing equilibrium constant of the iodine-benzene in cyclo-
hexane and heptane separately, the equilibrium constant of the iodine-heptane free
from other solvent can be computed which, in turn, allows to determine K, from
equcttion (9). The equilibrium constants of iodine complexes with other solvents are
calculated from this equation. The same procedure is followed to determine these
values in other temperatures. The results are reported in Table 2. The Fig. 2 shows
the absorption spectra. of iodine in benzene. With the help of the equilibrium con-
stant of the iodine-benzene complex, the molar extinction coefficient and oscillator
strength of the iodine-benzene complex are determined from these spectra of iodine
in benzene. The results are: E, = 11,600 and f = 0.262. The oscillator strength of
the benzene-iodine complex in different solvents (Table 1) is higher than this value
and the difference of these two values increases with the increase of the stability
of the iodine-solvent interaction. On the other hand, the stability of the iodine-
solvent interaction is relsted with the blue shift of the visible iodine band 1241.
Moreover, it has been seen that iodine solutions in these solvents except l,l-dichloro-
ethane chsnge the regular violet colour when these solutions are cooled at liquid
nitrogen temperature. As for example, iodine solution in methylcyclohexane forms
wine coloured glass at liquid nitrogen temperature, on warming it turns to violet
through pink. This is another evidence of forming iodine-solvent interaction. Thus
the iodine-solvent interaction plays an important role on the charge transfer complex
of benzene-iodine by increasing the charge transfer intensity with decrease of the
stability of the complex.
[22] 5. H. HASTINUS,J. L. FBANKLIN, J. C. SCEI- and F. A. MATSEN, J. Am. Clmn. Sot. 75,
2900 (1963).
[23] S. N. BEAT, K. R. BEWKAR and C. N. R. RAO, Proc. Indian Ad. Sci. 66A, 97 (1967).
[24] J. HABX,J. Am. Chem. Sot. 76, 3876 (1964).