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Journal of Molecular Liquids 157 (2010) 146150

Contents lists available at ScienceDirect

Journal of Molecular Liquids


j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m o l l i q

Polychloroprene degradation by a photo-Fenton process: The effect of solvent


Adonilson R. Freitas, Adley F. Rubira, Edvani C. Muniz
Grupo de Materiais Polimricos e Compsitos (GMPC), Departamento de Qumica, Universidade Estadual de Maring, Av. Colombo, 5790, 87020-970 - Maring, Paran, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The degradation of polychloroprene (PCP) by photo-Fenton process using FeCl36H2O and solvents with
Received 27 July 2010 different properties was studied by measuring the efux time in an Ubbelohde capillary viscometer. The
Accepted 18 September 2010 solvents benzene, toluene, chloroform, and THF (tetrahydrofuran) were investigated with regard to their
Available online 25 September 2010
inuence on the curves of efux time as a function of reaction time for the system exposed to light at a
constant temperature. PCP degrades in these conditions, and the phenomenon is strongly dependent on
Keywords:
solvent type. The degradation kinetics was also investigated based on efux time data. At short reaction times
Polychloroprene
Degradation
(0215 min), the curves of efux time vs. reaction time tted a second-order kinetic model for the different
Viscometry studied solvents. On the other hand, when the time interval was increased to 515 min, the adjustment was
Solvent property achieved only for curves obtained using THF and chloroform. The solvent properties, such as dielectric
constant, dipole and surface tension can be correlated with the efux time data collected for the PCP
degradation. The reaction proceeded faster in benzene when compared with the three other studied solvents.
2010 Elsevier B.V. All rights reserved.

1. Introduction change as well, and various aspects of the solvents inuence on PVC
disintegration rate in solution are observed [6]. In contrast, Al Ani et al.
Not until the 19th century did the effects of solvent on chemical [7] found that changes in solvent polarity have considerable effect on
processes become the subject of systematic studies, when the uorescence quenching, in spite of having a minor effect on the thermal
importance of understanding the roles played by solvents in the degradation of these polymers.
chemical equilibrium and rate of chemical reaction emerged. Thus, the This work has as its main objective the evaluation of the inuence of
effects of solvents on chemical processes were correlated with some of benzene, toluene, chloroform, and THF (tetrahydrofuran), as solvents,
their physical properties. In 1862, Berthelot and Saint-Gilles studied the on the degradation of polychloroprene by FeCl36H2O combined with
esterication of acetic acid with ethanol and discovered that some the exposure to light. The estimation of the photodegradation kinetic
solvents are capable of slowing down this process in spite of not actually parameters and correlation of the process to the solvent properties were
participating in the chemical reaction [1,2]. In 1890, Menschutkin, in a also objectives of this work.
classical study on the reaction of trialkylamines with haloalkanes using
23 different solvents, made clear how the choice of one or another 2. Experimental
solvent could substantially affect the reaction rate [3]. At that time,
Menschutkin [3] remarked that a reaction cannot be separated from 2.1. Materials
the medium in which it is performed. Experience shows that solvents
are capable of exerting considerable inuence on reaction rates. The In this study, commercial polychloroprene rubber samples
proper solvent or solvent mixture selection is important not only for (donated by Proquimil, Brazil) and FeCl36H2O (Aldrich) were used
chemical processes, but also for physical processes, such as recrystal- without further purication. Toluene and benzene were purchased
lization, all extraction processes, partitioning, chromatographic separa- from Synth (Brazil). Chloroform and THF were purchased from
tions, phase-transfer catalytic reactions, etc. [1,4,5]. Of particular Nuclear (Brazil). All solvents were of analytical degree. A commercial
interest in this context is the inuence of solvents on all types of light uorescent lamp (low pressure mercury and argon stream, 9 W) was
absorption processes, e.g., on UV/Vis, IR, ESR, and NMR spectra, caused used as a polychromatic light source.
by differential solvation of the ground and absorbing species in excited
states. According to Artsis and Zaikov [6], if the concentration of PVC in a 2.2. The solvent inuence in PCP-FeCl36H2O reaction
solution increases, the reaction rate of dehydrochlorination of PVC will
The inuence of solvent on the degradation of PCP was investigated
through efux time measurements performed using an Ubbelohde
Corresponding author. Fax: +55 44 3011 4125. suspended-level glass capillary viscometer, Cannon (100/E534). A 2.5%
E-mail address: ecmuniz@uem.br (E.C. Muniz). (wt./v) PCP solution was prepared by dissolving the polymer in a test

0167-7322/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.molliq.2010.09.004
A.R. Freitas et al. / Journal of Molecular Liquids 157 (2010) 146150 147

tube under stirring for 24 h. Four stock solutions were prepared, using a
proper solvent for each solution. A FeCl36H2O solution was prepared

Normalized efflux time (TR,510)


just before use by dissolving the solute in THF to obtain a conc. of 5%
0.5
(wt./v). Exactly 1.0 mL of this solution was joined to 10.0 mL of the PCP
solution (one of the four stock solutions) already placed in the
viscometer. After quick homogenization, the efux times were
measured every 15 min until the reaction time reached 510 min. The
0.4
experiment was repeated for each of the four solvents.

3. Results and discussion

0.3
3.1. Efux time measurements

Efux time measurement is a very useful technique for investi-


gating the degradation of polymers because, in general, the viscosity
of polymer solutions is higher than those of the respective low 0.2
THF Chloroform Toluene Benzene
molecular weight compound solutions when they have comparable
concentrations (mass/volume) of a given solvent. The high viscosity of Fig. 2. Normalized efux time at 510 min (TR,510) for PCP/FeCl36H2O degradation
polymer solutions is often due to the friction among the chains, and process on different solvents.

for a polymer of high molecular weight, it is mainly due to the


entanglements of polymer chains [8]. The large friction and the
increased amount of entanglements cause an increase in ow
efux times were different. Fig. 2 presents the efux times collected at
resistance and, consequently, in viscosity. In the absence of aggrega-
510 min (TR,510) for the four different solvents studied in this work.
tion effects, a reduction in the viscosity of a polymer solution, at a
Based on the efux time measured at 510 min (TR,510), the extent of
constant temperature, may be directly related to the degradation of
the degradation of PCP was ordered according to the solvent that was
the macromolecular chains [811]. Freitas et al. [11] showed that PCP
used, as follows (see Fig. 2):
can be degraded in a solution of toluene with FeCl36H2O when
combined with the exposure to polychromatic light. This reaction was
THF b Chloroform b Toluene b Benzene:
characterized as a photo-Fenton process [11].
Curves of efux time of PCP/FeCl36H2O in different solvents are
presented in Fig. 1. The efux times presented in Fig. 1 were Abdel-Bary et al. [12] studied the effect of the chemical structure of
normalized using Eq. (1), where Tt = 0 is the efux time before the the solvents (benzene, toluene, and xylene) on the photo-oxidation of
beginning of the reaction, i.e., t = 0 is the moment when the PCP in solution and veried that the photodegradation of PCP
FeCl36H2O/THF solution was poured into the viscometer that already proceeded more readily in benzene, as compared with toluene. In
contained the PCP solution. Tt and TR,t are the efux times measured at xylene, however, the reaction was slower than in toluene. According
time t and the respective normalized values. to Abdel-Bary et al. [12], this observation may indicate the
participation of solvent in the photo-induced reactions, resulting in
Tt = t a protective effect when the energy is transferred from excited
TR;t = : 1
Tt = 0 polymer molecules to the solvent, whereas a high quantum yield is
expected if the solvent transfers the excitation energy to the polymer
chains [12]. The chemical structure of the solvent determines which
The decrease in TR, t as the reaction time increased was correlated
reaction occurs more frequently, leading to either retardation or
to the extent of degradation. At reaction time t = 0, the value of TR,t
sensitization of the photodegradation process. Marconi et al. [13]
was 1.0, and it decreased gradually as the reaction time elapsed. PCP
studied the solvent effects on the photodegradation of a PPV [poly(p-
degraded with the four studied solvents; however, the decreases in
phenylene vinylene)] derivative [poly(3-methoxy-5-dodecyloxy-p-
phenylene-vynilene)], MD-PPV. For the four solvents studied in this
work (toluene, benzene, chloroform, and THF), it was veried that the
solvent polarity was not the only important factor. The chemical
1.0 THF nature of the solvent and polymerpolymer interaction may also have
Toluene an important role in the photodegradation process. Based on
Chloroform observations of Abdel-Bary et al. [12] and Marconi et al. [13], more
Noramalized efflux time

0.8 Benzene degradation was expected in benzene and less in THF, as conrmed in
this work, Fig. 2.

0.6 3.2. Evaluation of kinetics model for the PCP photodegradation

The chemical reaction rate is dened as being the change in the


concentration of a reactant or product per unit of time [14]. In this
0.4
study, the concentrations of the product do not appear in the rate law
because the reaction rate is studied under conditions in which the
reverse reactions do not contribute to the overall rate. The reaction
0.2 kinetics was studied by integration method. Freitas et al. [11] veried
0 100 200 300 400 500
that when polychloroprene was dissolved in toluene at the concen-
Reaction time (min)
tration of 2.5% (wt./v) and in the presence of FeCl36H2O, combined
Fig. 1. Normalized efux time as a function of reaction time for PCP/FeCl36H2O system with exposure to polychromatic light, the data of efux time vs.
on different solvents. reaction time tted well when the second-order kinetic model was
148 A.R. Freitas et al. / Journal of Molecular Liquids 157 (2010) 146150

used. According to the literature [14,15], the second-order kinetics did not adjust to this model. This is a strong indication of solvent
can be represented by a differential equation, as follows: dependence in the reaction kinetics. In spite of literature reports on
such linearity as being fortuitous, because of effects of factors, such as
dA 2 entanglements, in the efux time, such factor was not considered in
= kA : 2
dt this work. On the other hand, when the reaction time was reduced to
the interval of 0215 min and the data were treated with Eq. (5), the
Integrating this equation yields curves obtained for the four solvents were very well tted by the
second-order model (see Fig. 4).
1 1
= kt: 3 Analysis of Fig. 3 demonstrates that the photodegradation of PCP in
A A0
the presence of FeCl36H2O is dependent on the solvent. On the other
hand, Fig. 4 shows that all curves have linear adjustment when a
Taking A0 as the initial reactant concentration, (A0 x) is the
second-order model is applied. Comparison of Figs. 3 and 4 reveals a
concentration of the remaining reactant at time t, and k is the rate
new dependence in the reaction kinetics, the time-dependence. Thus,
constant, Eq. (3) can be rewritten as
we conclude that kinetic degradation of PCP by FeCl36H2O is
x dependent on four factors: i) polymer concentration and ii) light
kt = : 4 presence, as pointed out by Freitas et al. in previous work [11],
A0 A0 x
iii) solvent, and iv) reaction time, as pointed out in this work. Due to
By analogy, in this work, the following relations were used: A0 is the contribution of entanglements to the efux time data, as already
equivalent to 1.0; the value of x at reaction time t is equivalent to (1TR,t), discussed in previous papers [10,11], the slope of each straight line in
and the value of (A0 x) is equivalent to TR,t Then, Eq. (4) can be rewritten Figs. 3 and 4 can be related to the apparent rate constant.
as
  3.3. The inuence of solvent properties
1TR;t
kt = : 5
TR;t The PCP degradation process in the presence of FeCl36H2O was
described by Freitas et al. [11] as a photo-Fenton process. According to
The data set from Fig. 1 was treated with Eq. (5); the results are the literature, the photo-Fenton process is a reaction that occurs
presented in Fig. 3. almost exclusively in a liquid medium [16]. The type of solvent can
At the macroscopic level, a liquid is the ideal medium to transport considerably affect the rate and the kinetic order of a homogeneous
heat to and/or from exo- and endothermic reactions. From the chemical reaction. As early as 1890, Menschutkin demonstrated in his
molecularmicroscopic point of view, solvents can destroy the crystal classical study on the quaternization of triethylamine with iodoethane
lattice of solid moieties, dissolve gaseous or liquid reactants, and may using 23 different solvents that the rate of reaction varied remarkably
exert considerable inuence on reaction rates and the positions of with the choice of solvent. For instance, the reaction in n-hexane was
chemical equilibrium. Because of intermolecular forces (nonspecic four times slower than in diethyl ether, 36 times slower than in
or specic ones) acting among ions or molecules of dissolved benzene, 280 times slower than in methanol, and 742 times slower
reactants, the activated complexes, as well as the products and than in benzyl alcohol [2]. Thus, through judicious choice of solvent,
solvent molecules (leading to differential solvation of all solutes), the decisive acceleration or deceleration of a chemical reaction can be
rates, equilibrium and the selectivity of chemical reactions can be achieved. Fujita et al. [17] studied the degradation mechanism of 4-
strongly inuenced by the solvent [1,2]. The curves shown in Fig. 3 methacryloyloxy ethyl trimellitic acid, (4-MET). They veried that the
were obtained through application of a second-order kinetic model degradation 4-MET was strongly dependent on the type of used
[Eq. (5)] to the normalized data set of efux time presented in Fig. 1. It solvent. By studying the inuence of solvent polarity and the medium
was found that when the solvent used was chloroform or THF, the acidity on the UVvis spectral behavior of 1-methyl-4-[4-amino-
data set was very well tted by Eq. (5) and straight lines were styryl] pyridinium iodide, S.A. El-Daly et al. [18] veried that the
obtained. This is a strong indication that the reactions occurred uorescence quantum yield is also sensitive to the polarity and
through second-order kinetics, while in toluene and benzene, the data viscosity of the medium. By studying the solvent effect on thermal

3.5

1.6 THF
3.0 THF
Toluene
Toluene
Chloroform Chloroform
2.5 Benzene
Benzene 1.2
(1 - TR,t)/TR,t
(1-TR,t)/TR,t

2.0

1.5 0.8

1.0
0.4
0.5

0.0 0.0
0 100 200 300 400 500 0 50 100 150 200
Reaction time (min) Reaction time (min)

Fig. 3. Efux time data treated according to second-ordered kinetic [Eq. (5)] as a Fig. 4. Efux time data treated according to second-ordered kinetic [Eq. (5)] as a
function of reaction time under the 0515 min range. function of reaction time under the 0215 min range.
A.R. Freitas et al. / Journal of Molecular Liquids 157 (2010) 146150 149

Table 1 80
Solvent properties [19,20].

Extent of reaction (%) @ 510 min


Solvent Properties

Dielectric constant Surface tension Dipole


70
Benzene 2.28 28.90 0
Chloroform 4.80 27.16 1.10
THF 7.60 28.00 1.75
Toluene 2.38 28.50 0.40
60

degradation of plasticized p-substituted polystyrenes, Al Ani et al. [7]


veried that the change in the solvent polarity has a considerable
effect on uorescence quenching, despite the negligible effect on the
50
thermal degradation of these polymers. Quian et al. [19] observed that
the extension and type of upsweep or downsweep (anomalous
rheological behaviors) of reduced viscosityconcentration curves of 0.0 0.4 0.8 1.2 1.6
different polymers at high dilution are markedly dependent on the Dipole
dielectric constant and the polarity of the solvent used. In this sense,
the study of the inuences of solvents on chemical reaction is very Fig. 6. Extent of PCP degradation at 510 min as a function of dipole values for the
important. In this work, some properties of commonly used solvents solvents (the values of dipole are described in Table 1).
available in the literature [20,21] are described in Table 1.
Studying the photostability of ergocalciferol (vitamin D2) in Often, the activation energy depends on the type of reaction and
organic solvents, Ahmad et al. [22] veried that the photolysis does not vary rapidly from solvent to solvent [23]. The entropy of
reaction is inuenced by the solvent polarity and that an increase in activation is always negative and varies with the solvent, becoming
the dielectric constant leads to a decrease in the rate of reaction. In more negative as the polarity of the solvent decreases [23]. Reactions
this work, the inuence of the solvents on PCP degradation in the leading to products that are more polar than the initial substances, as
presence of FeCl36H2O, combined with exposure to polychromatic a rule, occur more rapidly in polar media. On the other hand, when the
light, was studied by measurement of efux time. The data were reaction products are less polar than the initial substances, a low-
correlated with solvent properties dielectric constant, dipole, and polarity solvent accelerates the reaction, as observed in the degrada-
surface tension. The extent of the degradation process was evaluated tion of polychloroprene in benzene (observe Fig. 1). Fig. 6 shows the
using Eq. (6). extent of degradation at 510 min (% of polychloroprene degradation,
TR,510) as a function of dipole constant of the four studied solvents.
  According to the HughesIngold theory [24] an increase in the
Degradation% = 1TR;t 100 6 solvating power of the medium accelerates the creation and
concentration of charges and inhibits their destruction and diffusion.
Thus a reaction in which the charges are not xed at a unique point,
where TR,t is the normalized efux time in the reaction time t. Values of but spread over the whole structure of transition state, will be slower
TR,t at a given reaction time t can be obtained from Fig. 1. The extent of in a better ion-solvating or polar solvent [25]. If the transition state is
degradation at 510 min in the four studied solvents given solvent (% of less polar than the initial (or fundamental) state, an increase in
polychloroprene degradation, TR,510) as a function of dielectric constant solvent polarity will increase G (free energy) and decrease the
was plotted in Fig. 5. As the dielectric constant of the solvent increases, a reaction rate [26]. This may be true for the photodegradation behavior
decrease in the extent of PCP degradation occurs. Such behavior was also of polychloroprene, for which an increase in solvent dipole leads to a
veried by Ahmad et al. [22] studying the photostability of ergocalciferol decrease in the rate of reaction and may, therefore, imply the
(vitamin D2) in organic solvents. existence of a non-polar or a less polar transition state, as compared
with the initial state. Such a transition state will be destabilized by an
increase in solvent polarity, and its rate of reaction will be decelerated.
80 A reaction type of the present case (photodegradation of PCP in the
presence of FeCl36H2O combined with exposure to polychromatic
Extent of reaction (%) @ 510 min

light) will proceed more rapidly with a decrease in solvent polarity, as


indicated by the ratereciprocal dielectric constant relationship. In
70 addition to alterations in activity coefcients of the reactant molecules
and the transition state, changing the solvent system may bring about
concomitant changes in surface tension and viscosity, thus indirectly
affecting the reaction rate [27]. Surface tension (), viscosity (), and
60 thermal conductivity () are classied as surface () and transport
properties ( and ) of materials. The magnitudes of these properties
depend on intermolecular interactions [27]. These interactions dictate
the surface elasticity and the ow and the miscibility of two phases, as
well as the ability of the liquid to dissipate temperature uctuations
50
during reaction [27]. Therefore, the solvent viscosity may inuence
the diffusion processes and hence the rate of reaction [28]. A
2 4 6 8 consideration on the inuence of solvent viscosity on the rate of
oxidation reaction may be necessary, as the viscosity of a liquid affects
Dieletric Constant
the rate at which molecules diffuse through the solution, which, in
Fig. 5. Extent of PCP degradation at 510 min as a function of dielectric constant values turn, affects the rate of oxidation of sensitive compounds at the liquid
for the solvents (the values of dielectric constant are described in Table 1). surface [29]. A plot of extent of degradation (%) of PCP as a function of
150 A.R. Freitas et al. / Journal of Molecular Liquids 157 (2010) 146150

80 in other solvents. Compared with the three other solvents, benzene


presents lower dielectric and dipole constants and higher surface tension.
Extent of reaction (%) @ 510 min

Acknowledgements
70
The authors thank the Conselho Nacional de Desenvolvimento
Cientco e Tecnolgico (CNPq-Brazil), Grant no. 309005/2009-4) and
Coordenao de Aperfeioamento Pessoal de Nvel Superior (CAPES-
60 Brazil) for nancial support.

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