Chapter 23
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Mechanisms Controlling Chlorocarbon Reduction at Iron Surfaces Tie Li and James Farrell* Department of Chemical and Environmental Engineering, University of Arizona, P.O. Box 210011, Tucson, AZ 85721
Abstract: This research investigated whether rates of carbon tetrachloride (CT) and trichloroethylene (TCE) dechlorination on iron surfaces are limited by rates of electron transfer. The contributions of direct electron transfer and indirect reduction via atomic hydrogen to the overall dechlorination rates were also investigated. Electron transfer coefficients for C T and T C E were determined from measurements of dechlorination rates over a potential range from -600 to -1200 m V (SHE), and a temperature range of 2 to 42 °C. The transfer coefficient for C T was found to be independent of temperature, and the apparent activation energy was found to decrease with increasingly negative electrode potentials. These observations indicate that the rate of electron transfer controlled the observed rate of C T dechlorination. In contrast, the transfer coefficient for T C E was temperature dependent, and increased with increasingly negative electrode potentials. This indicated that T C E dechlorination was not controlled by an electron transfer step. Comparison of analytically and amperometrically measured reaction rates showed that C T reduction occurred primarily via direct electron transfer, while T C E reduction involved both direct electron transfer, and an indirect mechanism involving atomic hydrogen. Comparison of amperometrically
© 2002 American Chemical Society
397
398 and analytically measured reaction rates for T C E and perchloroethylene (PCE) also supports an indirect mechanism for chloroethene reduction.
Introduction Chlorinated organic compounds are prevalent groundwater contaminants due to their widespread use as industrial solvents. Because many of these compounds are classified as carcinogens or suspected carcinogens, chlorocarbons must be removed from drinking water supplies prior to potable use. Presently employed remediation technologies include adsorption by activated carbon and air stripping. While these methods are effective for removing chlorocarbons from the aqueous phase, they only transfer the contaminants from water to another medium, which then requires treatment or disposal In recent years there has been considerable interest in developing destructive treatment methods for removing chlorinated organic compounds from contaminated waters. The use of zerovalent metals for reductive dechlorination has been a veiy active research area since Gillham and O'Hannesin (7) proposed that metallic iron filings could be utilized in passive groundwater remediation schemes (2-72). In zerovalent iron remedial systems, the iron serves as an electron donor to reduce chlorinated organic compounds to their nonchlorinated analogs and chloride ions. Redox active metals, water itself, and other groundwater constituents, such as nitrate and carbonate, may also be reduced by reactions with the zerovalent iron (13, 14). Several possible reaction mechanisms for reductive dechlorination at zerovalent iron surfaces are illustrated in Figure 1. Direct reduction may occur via electron tunneling to a physically adsorbed chlorocarbon, or through a chemical bond to a chemisorbed species (75, 16). Arnold and Roberts postulated that chloroethenes form chemisorption complexes with iron as depicted in Figure 1 (75, 16). Chlorocarbons may also be reduced indirectly via reaction with atomic hydrogen produced from water reduction (77). These reactions may involve formation of hydride-chlorocarbon complexes (75). For reactions involving atomic hydrogen, the iron acts as a catalyst for both the water reduction reaction and the dehalogenation reaction. This electrocatalytic hydrodechlorination mechanism has been found to operate in palladium catalyzed systems used for reductive dechlorination (18-21).
399 Dechlorination rates and byproducts for most environmentally relevant chlorocarbons have been determined under a wide range of experimental conditions (1-13, 16). Chlorinated alkane reduction by zerovalent iron has been found to proceed sequentially, and produces chlorinated products (3). For example, dechlorination of carbon tetrachloride (CT) produces primarily chloroform as the first stable product (3). In contrast, chlorinated alkene reduction yields primarily completely dechlorinated species as the first stable products. For example, dechlorination of perchloroethylene (PCE) and trichloroethylene (TCE) has been hypothesized to involve a β-elimination mechanism that yields chloroacetylene as the first detectable product (4, 16). However, the chloroacetylene is unstable and is rapidly reduced to acetylene and ethene, and has therefore not been reported by most investigators (4, 5, 16).
CI
Direct Electron
CI-C-CI I Cl t
T
r
a
n
S
f
C
Indirect Electron
r
Transfer Cl H
Cl H
II
ι
c i — ç - ç - c i
"Τ \ β" ^ tunneling to physically
Fe
Fè
^
v
Ν g "
chemisorbed species
IrOIl
adsorbed species
I
ci—Ç-_£-CI H
.
reaction with adsorbed atomic hydrogen
Figure 1. Possible reaction mechanisms for reductive dechlorination at zerovalent iron surfaces. Although most investigators have reported faster dechlorination rates with increasing degree of halogenation, not all studies are consistent with this trend. For example, Arnold and Roberts (16) reported that dechlorination rates for a series of chlorinated alkenes decreased with increasing degree of chlorination, and Farrell et al. (9) reported faster rates of T C E dechlorination than for P C E . These observations suggest that there is an indirect mechanism involved in chloroethene reduction. Rates of multistep electron transfer reactions are dependent on potential according to the Butler-Volmer equation, as given by (22, 23): .
.
r
i = i [e 0
-aF(E-E
)/RT eq
aF(E-E
-e
)/RT eq
η
]
(1)
400 where ζ is the net reaction current, i is the exchange current, F is the Faraday constant, R is the gas constant, Τ is temperature, Ε is electrode potential, E is the equilibrium potential for the overall redox reaction, and à and à are the transfer coefficients for the reduction and oxidation reactions, respectively. The first term in brackets represents the rate of the forward reduction reaction, while the second term gives the rate of the reverse oxidation reaction. The transfer coefficients depend on the number of electrons transferred before and after the rate determining step, and whether the rate determining step involves electron transfer (25). 0
eq
One purpose of this investigation was to determine whether the rate determining step for C T and T C E reduction involves electron transfer. A second goal of this research was to determine the contribution of direct and indirect reduction mechanisms to the overall rate of T C E and C T dechlorination.
Materials and Methods Voltammetric Experiments Voltammetric analyses using chronoamperometry (CA) and Chronopotentiometry (CP) were performed in a custom three-electrode cell using an E G & G (Oak Ridge, TN) model 273A potentiostat and M270 software. A l l controlled potential or controlled current experiments utilized an E G & G model 616 rotating disk electrode, a H g / H g S 0 reference electrode, and a platinum wire counter electrode encased in a proton permeable membrane (Nation, Dupont). A n iron disk (Metal Samples Company, Mumford, A L ) was used as the working electrode. The experiments were conducted in 10 m M C a S 0 background electrolyte solutions that were deoxygenated during and prior to use by purging with argon or nitrogen. 2
4
4
The C A and C P experiments were performed at constant halocarbon concentration by purging the solution with nitrogen gas containing C T or T C E for the duration of each experiment. Prior to each experiment, the iron disk was polished with an E G & G polishing kit, and conditioned at -785 m V with respect to the standard hydrogen electrode (SHE). After a one hour conditioning period, the applied potential was momentarily terminated before applying the fixed potential for each C A experiment. In order to maintain cathodic cell currents, the C A experiments were performed only at potentials below the open circuit potential of the iron disk. The uncompensated resistance between the working and reference electrodes was 20 Ω. Since the cell currents were less than 200 μΑ in ail experiments, the maximum voltage loss due to
401 solution resistance was less than 4 mV. A l l potentials are reported relative to the standard hydrogen electrode, and cathodic currents are reported as positive. Experiments with freely corroding iron were performed i n a 25 mL, air tight glass cell. A single iron wire (Aesar, Ward H i l l , M A ) was used as the reactant. Iron corrosion rates were determined from analysis of Tafel diagrams produced by polarizing the iron wire electrodes ±200 m V with respect to their open circuit potentials. These experiments utilized a platinum wire counter electrode and a A g / A g C l or H g / H g S 0 reference electrode. 2
4
Analyses T C E , P C E and C T concentrations i n all solutions were determined by analysis of 100 μ ι aqueous samples. The 100 μ ι samples were injected into 1 g of pentane and analyzed by injection into a Hewlett-Packard 5890 Series II gas chromatograph equipped with an electron capture detector and autosampler. Chloride ion concentrations were determined by analysis of 5 mL samples using a D X 500 ion chromatograph (Dionex, Sunnyvale, CA). A n Orion p H probe was used to determine the initial and final p H values of the electrolyte solutions.
Chronoamperometry Profiles Chronoamperometry profiles for an iron electrode i n a blank electrolyte and in electrolyte solutions containing 2 m M C T or 4 m M T C E are shown i n Figure 2. In the C T solution, there is an increase i n current compared to that i n the blank electrolyte. This increase in current is equal to the C T reduction current determined from a chloride balance on the solution. This indicates that C T dechlorination occurred via direct electron transfer. In contrast to C T , the presence of T C E in the solution resulted in a decrease in current compared to the blank electrolyte. This indicates that T C E on the electrode surface interfered with water reduction, and that T C E was reduced more slowly than water at an electrode potential of -780 mV. The apparent independence of C T and water reduction can be attributed to a low adsorbed surface coverage of C T on the electrode. The amount of C T adsorbed on the electrode surface was determined from an Anson analysis of early time C A profiles for blank and C T containing solutions (22). The charge transferred during the first 0.1 seconds of C A profiles for blank and C T solutions is shown i n Figure 3. For the time span shown i n Figure 3, virtually all the current was due to electrical double-layer charging and to reduction of compounds adsorbed on the electrode surface before the start of the experiment.
402 The similar slopes of the two profiles in Figure 3 indicates that the double-layer charging currents were the same i n the blank and C T containing solutions. The 15.5 μΟ difference in intercepts between the two profiles was due to reduction of C T adsorbed on the electrode surface under open circuit conditions (22). Assuming a surface area of 0.32 n m for each adsorbed C T molecule, only 15% of the 1 c m geometric electrode surface area was covered with adsorbed C T under open circuit conditions. However, since the geometric surface area ignores molecular scale roughness, and thus underestimates the surface area available for adsorption, the actual portion of the iron surface covered with adsorbed C T may be significantly less than 15%. 2
2
10000 -r
10
-J
1
1
1
i
1
0
2
4
6
8
10
Time (sec) Figure 2. CA profiles at a potential of-780 mVfor an iron electrode in a blank 10 mM CaS0 electrolyte solution and in electrolyte solutions with 2 mM CT or 4 mM TCE. 4
Although the adsorbed surface coverage of C T was much less than one monolayer at an aqueous concentration of 2 m M , reaction rates for C T deviated from pseudo-first order kinetics at concentrations below 0.2 m M . Figure 4 shows that the rate of C T reduction (RCT) did not increase in a linear fashion with the C T concentration. This indicates that C T reduction was not first order in C T concentration. For surface mediated reactions, this type of behavior is normally indicative of reactive site saturation effects. Previous investigators have observed that C T reduction by corroding zerovalent iron also deviates from pseudo-first order kinetics at C T concentrations as low as 100 μΜ (6). A s suggested by the data in Figure 3, C T concentrations in this range would be associated with adsorbed surface coverages less than 1% of a monolayer. This behavior suggests that there are vaiying reactivities for different areas of the iron surface.
403
0.1
0.4
0.3
0.2 1 2
1/2
t ' (sec ) Figure 3. Anson analysis of CA profiles generated by an iron electrode at-985 mVin 10 mM CaS0 solutions, with and without 2 mM CT. At time=0, the electrode potential was stepped from its open circuit potential of-565 mV (blank) or -482 mV (CT) to -985 mV. 4
1
2
3
4
Concentration (mM) Figure 4. Reaction rate for dechlorination of CT to chloroform by a rotating disk electrode at a potential of -635 mV as a function of the bulk solution concentration.
404 This variation i n surface reactivity can likely be attributed to molecular scale heterogeneity of the electrode surface. It is well known that rates of electron transfer on electrode surfaces vary depending on the crystal face (23). For corroding iron systems, corrosion rates are known to vary with location on the iron surface due to crystal defects, grain boundaries, stress differences and surface energy effects (24).
Transfer Coefficient Analysis In multistep electron transfer reactions, the overall reaction rate may be limited by rates of reactant chemisorption, rates of bond breaking, or rates of molecular rearrangement. These are chemical, rather than potential, dependent factors. If the observed reaction rates are limited by chemical dependent factors, the measured transfer coefficients may be only fitting parameters, or apparent transfer coefficients. In this case, the apparent transfer coefficient will be temperature dependent (25-27). Conversely, for reactions that are limited by potential dependent factors, i.e., the rate of outer-sphere electron transfer, the transfer coefficient should be independent of temperature (25-27).
Figure 5. Electron transfer coefficients for reductive dechlorination ofCTand TCE by an iron disk electrode. Transfer coefficients were determined using equation 1 and measured rates of dechlorination over the potential range from -600 to -1200 mV.
405 To determine whether the rate limiting step for C T reduction involved electron transfer, the transfer coefficient for C T reduction was determined over the temperature range from 2 to 42 °C. Figure 5 shows that the transfer coefficient for C T reduction was independent of temperature, at the 95% confidence level. This suggests that the rate of electron transfer controlled the rate of C T dechlorination. Further supporting this conclusion is the temperature dependence of the apparent activation energy (E ) for C T reduction. Figure 6 shows that the apparent activation energy for C T reduction decreased with decreasing electrode potential. This is consistent with electrochemical theory which predicts that a fraction of the overpotential (EE ) goes towards overcoming the chemical activation energy (23). Thus, for an electron transfer reaction, the apparent E should depend on the electrode potential according to (25): a
eq
a
+
(2)
aF(E-EJ
e q
where E a is the activation energy at the equilibrium potential. In this study, all overpotentials for C T reduction were negative, and thus E values decreased with increasingly negative electrode potentials. a
60 τ
c
ε τ
0)40 Ο
α α ο -0.6
-0.8
-1
-1.2
E(VSHE) Figure 6. Apparent activation energies for reductive dechlorination of CT at an iron electrode. Activation energies were determined from Arrhenius analysis of dechlorination rates at temperatures of2, 12, 22, 32 and 42 ° C
406 In contrast to C T , the transfer coefficient for T C E reduction was temperature dependent at the 95% confidence level, as shown i n Figure 5. This suggests that the rate of T C E reduction was not limited by an electron transfer step. The temperature dependence of the E for T C E reduction shown in Figure 7 also supports this hypothesis. If the rate of T C E dechlorination was limited by the rate of electron transfer, the E should have declined with increasingly negative potential, as indicated by equation 2. a
a
60 -r
TCE
[
11 CO
ï 4 s-4-Î L
1[ — - — J r~02 _
r*
or*
R = 0.26
^
α 1.20 < -0.6
-0.8
-1.2
E(VSHE) Figure 7. Apparent activation energies for reductive dechlorination of TCE at an iron electrode. Activation energies were determined from Arrhenius analysis of dechlorination rates at temperatures of 2, 22, and 42 °C.
Direct and Indirect Reduction Comparison of amperometrically with analytically measured reaction rates for T C E and P C E suggest that there was an indirect mechanism involved in chloroethene reduction. Figure 8 shows the current going towards T C E and P C E dechlorination via direct electron transfer. Assuming a 6 electron transfer for T C E dechlorination and an 8 electron transfer for P C E , the currents for direct reduction at a concentration of 0.9 m M indicate that the direct reduction rate for P C E should have been 5 times faster that that for T C E . However, analytical determination of the rates of T C E and P C E dechlorination indicate that the rate constant for P C E reduction was only 2.8 times that for T C E . This suggests that in addition to direct electron transfer, there is an indirect reaction
407 mechanism that is faster for T C E than for P C E . This mechanism likely involves reaction with atomic hydrogen produced from water reduction.
Concentration (mM) Figure 8. Corrosion current (l ) associated with TCE and PCE reduction via direct electron transfer from an iron wire suspended in a 10 mMCaS0 electrolyte solution with either TCE or PCE present at the indicated concentrations. corr
4
The indirect reduction mechanism becomes increasingly more important with decreasing solution concentration. For example, at aqueous concentrations of 0.01 m M , the overall rate for T C E dechlorination was 20% faster than that for P C E . This indicates that the relative rates of T C E and P C E dechlorination depend on the concentration range, and further supports the hypothesis that there are two reaction mechanisms for dechlorination. The concentration dependence of the indirect reduction mechanism for T C E can be understood from the data in Figure 9. At low T C E concentrations, there is sufficient atomic hydrogen produced from water reduction to measurably contribute to T C E dechlorination. For example, Figure 9 shows that at concentrations less than 1 m M , the current for water reduction was greater than the direct current for T C E reduction, whereas, at higher T C E concentrations, the water reduction current was small compared to the direct reduction current for T C E .
408 2
-r
0
2
4
6
TCE concentration (mM) Figure 9. Total corrosion current, water reduction current and direct TCE reduction current for an iron wire electrode suspended in a 10 mMCaS0 background electrolyte solution as a function of the TCE concentration. 4
The results presented in Figures 8 and 9 may help explain some apparently contradictory data i n the literature. Although most investigators have reported faster rates of P C E versus T C E dechlorination (2), one investigation reported significantly faster rates for T C E dechlorination (16). Arnold and Roberts reported that reaction rates for a series of chlorinated ethenes decreased with increasing degree of halogenation, a trend contrary to virtually all previously reported data (2). These apparently contradictory results may be explained i n terms of direct and indirect reaction mechanisms. The Arnold and Roberts study was conducted at veiy low concentrations (in the 1-100 μΜ range), whereas other investigators have conducted their studies i n the 0.1 to 10 millimolar range. A t low concentrations, indirect reduction by atomic hydrogen is the dominant reaction pathway, while the direct reduction mechanism dominates at high chlorocarbon concentrations. This hypothesis is supported by data from the Arnold and Roberts study which showed that T C E and P C E reaction rates decreased with increasing concentration, and the ratio of the T C E rate constant to that for P C E decreased with increasing concentration (16). For example, at a concentration of 4 μΜ, the rate constant for T C E was 12 times greater than that for P C E , while at 80 μΜ, the difference was only a factor of 7. The fact that less chlorinated compounds react faster via the indirect mechanism is consistent with studies of chlorocarbon dechlorination by atomic hydrogen in palladium catalyzed systems (18, 19). This may be due to the fact
409 that less chlorinated compounds are more easily chemisorbed than are more chlorinated homologues. Decreasingly favorable chemisorption with increasing halogenation may be attributed to repulsions between the negatively charged chlorine atoms and electrons in the metal surface. This hypothesis is supported by studies of ethene hydrogénation on metal surfaces. Ab initio modeling indicates that the energy barrier for chemisorption is dominated by repulsions between electrons in the hydrocarbon and those i n the metal surface (28). Results from this study indicate that reduction of C T involves direct electron transfer, and that the rate of electron transfer controls the C T dechlorination rate. In contrast, reaction of T C E involves both direct and indirect reduction mechanisms, and the rate determining step does not involve electron transfer. The indirect reduction mechanism for T C E is faster than the direct mechanism, but its contribution to the overall rate of dechlorination decreases with increasing concentration.
Acknowledgment This research has been supported by the United States Environmental Protection Agency (USEPA) office of Research and Development. Although the research described i n this article has been funded by the U S E P A through grant R-825223-01-0 to J.F., it has not been subjected to the Agency's required peer and policy review, and therefore does not necessarily reflect the views of the Agency, and no official endorsement should be inferred.
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