Environ. Sci. Techno/.
1995, 29, 1511-1517
Destruction of Organohalides in
Water Using Metal Particles:
Carbon TetrachloridelVVater
Reactions with Magnesium, Tin,
and Zinc
TATYANA BORONINAt A N D
KENNETH J. KLABUNDE*
Department of C h e m i s m , Kansas State University,
Manhattan, Kansas 66506
GLEB SERGEEV
Department of C h e m i s m , Moscow State University, Moscow,
Russia 119899
As a possible method for degrading chlorocarbons
in contaminated water supplies, the reactions of metallic
magnesium, tin, and zinc with CCIdH20 mixtures have
been studied. In the case of Mg, oxidation by water
overwhelmed the Mg-CC14 reaction. However, Sn
and Zn were successfully used to degrade CC14. Major
products in the Sn/CCIdH20 system were CO2, CHC13,
SnOz, and HCI with smaller amounts of CHC13 and
CH2C12. In the case of Zn/CCI$H20, the major products
were ZnC12,Zn(OH)2, and CH4 with CHC13, CH2C12, and
CH3CI as intermediate products. Thus, Sn and Zn
behave quite differently with the final carbon-containing
product, with Zn being CH4 but with Sn being COZ.
This is rationalized by the competing reactions of a
possible intermediate CI$MCI, which can be pro-
tonated by H20 to give CHC13 or eliminate CC12 (which
subsequently reacts with water to form CO2 and HCI).
Metal surface areas are also important, and the
most active metal samples were prepared by a metal
vapor-solvent codeposition method (SMAD cryo-
particles). However, conventional Zn dust and Sn
granules were also effective, onlywith lower reaction
rates.
0013-936X/95i0929-1511$09.00/0 3 1995 American Chemical Society
c VOL. 29, NO. 6, 1995 i ENVIRONMENTAL SCIENCE & TECHNOLOGY
Introduction
Background Literature. Gillham and O’Hannesin (1)and
Reynolds and co-workers (2)have reported on the trans-
formations of halogenated aliphatic compounds in the
presence of metallic particles of several metals (especially
transition metals). In particular, iron (steels), galvanized
metals, aluminum, copper, and brass were studied. Their
intriguing studies showed that in some cases over an 80%
decline in the concentration of chlorocarbon occurred over,
for example, 336 h. Galvanized metal (zinc)and mild steel
consistentlygave the highest rates of degradation, and 50%
reductions in chlorocarbon concentrations were sometimes
found in as little as 45 min (3).
These very encouraging results prompted our interest
in exploring the underlying chemistry involved and in
finding metal samples that would completely detoxify the
chlorocarbon (rather than convert it to another toxic
compound). In fact, several research groups have taken
up this challenge as judged by very recent presentations
(4-6). Herein, we describe some results utilizing Mg, Zn,
and Sn metals. Earlier work has employed primarily zero-
valent iron. At this time, it is not our intent to evaluate
which metal system would be preferable from an economic
or even environmental standpoint. Instead, our studies
are aimed at gaining some chemical understanding at how
different metals behave when reactingwith chlorocarbonl
water mixtures.
Further Rationale. The chemistry of metals reacting
with chlorocarbons in aqueous solution is a rather new
concept for chemists. In the past, it was generally thought
that water would preclude such chemistry. Indeed, ever
since the time of Frankland (7) and Barbier (81, the reactions
of organohalides with metals have been of great interest
and usefulness, but an important tenant of this work was
to avoid water contamination at all costs, otherwise either
the reactions could not be initiated or the products would
be destroyed.
However, as we have seen, recently a different thought
process has been necessary. Due to long-term widespread
use of chlorocarbons in commerce and industry, there are
huge quantities of groundwater that are now contaminated
bychlorocarbons. It is becoming clear that new approaches
need to be developed for the decontamination of these
water supplies, either in-situ or by pump-and-treat meth-
ods.
Ultrafine metal particles offer a promising new approach
to this problem. Their high reducing potential is a desired
property since the contaminants (organohalides, nitro
compounds, etc.) generally have reasonably high electron
affinities. For example, we can consider the zinc/CCL
reaction from a thermodynamic point of view:
2zn(s) + CC1,(1) - 2ZnCl,(s) + C(s) (1)
AH- = -702 kJ
This is a very exothermic reaction. However, under the
circumstances described, there are two problems: (1) this
is a solidlliquid reaction, and so surface area and possibly
t Visiting scientist from Moscow State University, Moscow, Russia,
supported by the National Science Foundation.
1511
morphology of the metal would play a major kinetic role,
and (2) water will be present.
Of course, water potentially changes reaction pathways
in significant ways. Metals with high reducing potentials
are often thermodynamically unstable in water, e.g.
AH- = -70 kJ
The thermodynamics of such reactions is only one con-
sideration. The reacting metal particles can form protective
hydroxide and/or oxide layers that can inhibit even the
most thermodynamically favorable processes. Thus, in
order for a reaction to be successful, CCL must be able to
penetrate this forming oxidelhydroxide layer and thereby
continue to react at a rate higher than the metal can react
with water itself. In addition, water could become involved
in the chemistry secondarily as a medium for transport of
intermediates or products away from reactive metal sites
or by direct participation by providing protons. For
example, we know that in organic solventscarbon-halogen
-
bonds often oxidatively add to zero-valent metals (R-X
M R-M-X, especially where M = Mg or Zn) (9). It is also
known that CCL can behave similarly but that C13CMC1
usually is unstable, decomposing thermally to CC12+ MC12.
In fact, compounds such as C ~ ~ C H ~ C are~ very
H S useful as
CC12 transfer reagents (10). Thus, it seems feasible that a
short-lived intermediate such as shown in reaction 3 could
be involved and that rapid protonation or carbene elimi-
nation could direct the reaction in different ways:
+ H,O
- + HOZnCl
C1,CH
C1,CZnCl
- C02 + ZnC1, + 2HC1
With this background,we will now describe the initial results
with Mg, Sn, and Zn reactions with CCLlH20 mixtures.
Experimental Section
ReactantslSolvents. Distilled water; carbon tetrachloride,
spectranalyzed grade (Fisher Chemical/Fisher Scientific);
chloroform, 99.9% ACS, HPLC grade (Aldrich);methylene
chloride, analytical grade (Fisher Chemical/Fisher Scien-
tific); magnesium metal, ribbon, m-8 (Fisher Scientific);
tin, metal, mossy, reagent ACS, Code 2390 (Baker and
Adamson); tin, metal, granular, analyzed grade 0. T. Baker
Chemical Co.);and zinc, metal dust (FisherScientific),were
used to conduct the reactions between chlorocarbon and
metal particles in water solution. Magnesium ribbon was
cut into small pieces just prior to use, washed with acetone,
and dried. Tin and zinc metal particles were used without
any treatment. Surface areas for these metal samples were
quite low ( < I m2/g).
High Surface Area Metal Samples. In order to be able
to compare extremely reactive metal powders with con-
ventional samples, a metal vaporization procedure was
employed. The method has been described elsewhere (11,
12) and has been called the SMAD method or the cry0
method.
Synthesisof Zn and Sn Cryo-Particles. Cryo-particlesof
Zn and Sn were prepared by codeposition under vacuum
(1 x Torr) of the vapors of 2.5 g of the metal with 150
mL (liquid) of pure pentane at 77 K over a 1-2-h period.
After completion of the codeposition, the pentane was
pumped away under vacuo, and the cryo-particles were
1512 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 6 , 1 9 9 5
collected and stored under argon gas. Surface areas are
generally between 30 and 60 m21g.
General Procedure for Reaction of Metal Particleswith
Chlorocarbon and Water. Distilled water (100 mL) was
placed into a 250-mL two-neck round-bottom flask, and
argon was bubbled through it for at least 4 h, but usually
overnight. Metal [2-5 g (0.08-0.2 mol) of magnesium, 1
or 10 g (0.008 or 0.08 mol) of tin, 1 or 5.2 g (0.015 or 0.08
mol) of zinc] was added under a flow of argon, and the flask
was sealed immediately with a Teflon-faced silicon rubber
septum. Chlorocarbon (100pL) was injected through the
septum under the water level. The reaction mixture was
magnetically stirred at room temperature. The reaction
flask was covered to avoid chlorocarbon decomposition
due to the light.
When the experimentwith cryo-particleswas conducted,
1 g of tin or zinc cryo-particles was placed into the flask in
a dry cabinet under argon. Then the flask was sealed with
a septum and taken out; 100mL of distilled water saturated
with argon (argon was bubbled through water overnight)
was injected into the reaction flask through the septum,
and 1OOpLof chlorocarbon was added with a syringe under
+
the water level.
Reaction headspace and water solution were sampled
through the septa and analyzed by GC, GClMS, and FT-IR.
Solid products [Mg(OH)2,Zn(OH),, Sn02]were analyzed
by X-ray diffraction (XRD).
Gas Chromatography/MassSpectrometry(GC/MS) and
GCAnalyses. To identify gaseous and liquid products such
as chloroform, methylene chloride, and methyl chloride in
a single injection over the course of the reaction, GClMS
analysis was performed. The reaction headspace was
analyzed by a Hewlett Packard GUMS system (5890 Series
(3)
I1 GCl5989A mass spectrometer) using an RTX-5 capillary
column (Alltech, 5% diphenyl polysiloxane and 95% di-
methyl polysiloxane),30 m x 0.25 mm i.d. x 0.25 pm film
thickness. The column temperature was 35 "C, the injection
port temperature was 230 "C, the flow rate was 30 mLlmin,
and the split was 1:30. For each analysis, 1OOpLof reaction
headspace was injected using a gas-tight syringe.
The water solutions were analyzed by a Perkin-Elmer
GUMS system (Auto System Gas ChromatographlQ-Mass
910 Mass Spectrometer). An HP-1 (cross-linked methyl
silicon gum) capillary column, 1.2 m x 0.2 mm i.d. x 0.33
pm film thickness, was used. The analysis conditions for
direct water injection were column temperature 90 "C,
injection temperature 230 "C, flow pressure 10 psi, split,
the AUX zone temperature 200 "C, the sample volume 1pL.
Gas chromatographic analysis was used to observe chlo-
rocarbon degradation and appearance ofliquid and gaseous
products-chloroform, methylene chloride, dichloroethane,
carbon dioxide, methane, and methyl chloride. The GC
analyses were carried out on the Series 580 GOW-MAC
isothermal gas chromatograph with thermal conductivity
dector (TCD) and argon as the carrier gas. For these
analyses, 200 pL of reaction headspace or 1 pL of water or
pentane solutionwas injected. Agas-tight syringewas used
for headspace injections.
For headspace analyses of volatile chlorocarbons, an
Alltech 2.4 m x 3.2 mm x 2.2 mm i.d. stainless steel, Teflon-
coated column packed with 1%ATIM-lOOOon Graphpac-
GB, 60l80 mesh, was used. The column temperature was
115 "C, the injection port temperature was 200 "C, and the
detector temperature and the current were 120 "C and 120
mA, respectively. The carrier gas flow rate was 30 mllmin.
 The measurements of the concentration of carbon
dioxide generated over the reaction were carried out using
anAlltechTELON 1.8m x 3.2mmo.d. x 2.4mmi.d.column
packed with Chromosorb 107,801100 mesh. The column
temperature was 76 "C, injector temperature was 200 "C,
and the detector temperature and current were 100 "C and
120 mA, respectively, while the flow rate was 30 mL/min.
The appearance of methane was detected by a Carbo-
sphere, 80/100 mesh column, Alltech, stainless steel, 3 m
x 3.2 mm x 2.2 mm. The column temperature of 120 "C,
the injector temperature of 200 "C, detector temperature
of 140 OC, a detector current of 120 mA, and a flow rate of
40 mL/min were used for these measurements.
Portions of the water layer were analyzed by extraction
with pentane (22 mL of water and 3 mL of pentane), and
portions of the pentane extract were analyzed using a 3.7
m x 3.2 mm 0.d. x 2.2 mmi.d. stainless steel column packed
with 10% UCON-50-HB-5100on Chromosorb W-HP, 801
100 mesh. The column temperature was 90 "C, injector
temperature was 200 "C, detector temperature was 120 "C,
detector current was 120 mA, and the flow rate was 20 mLI
min.
fl-hfiared (PT-IR) Measurements. The infrared trans-
mission spectra were recorded at 2 cm-' resolution and
signal averaging of 64 scans using a Bio-Rad FT-IR
spectrometer (FTS-40). A homemade IR-gas cell of 10 cm
length and 1.5cm diameter, equipped with a stopcock, was
used to obtain FT-IR spectra of the reaction headspace.
The cell was evacuated to Torr, and the background
spectrum was recorded. Then 2-20-mL portions of head-
space gas were injected through the septum and the
spectrum of headspace obtained.
X-rayPowder Diffraction (XFtD)Analysis. X-ray powder
diffraction data were collected on a Scintag-XDS-2000
automatic diffractometer (Cu KQ radiation) set at voltage
of 40 kV and a current of 40 mA. The range 20-80" 2 0 and
the scanning speed 2" 2 0 min-' were used to obtain the
diffractometer trace for solid product identification.
To measure the diffraction peak broadening due to the
small cryo-particle size, scans ranged from 40" to 46" 2 0
for zinc and from 42" to 48" 2 0 for tin with the scanning
speed 0.02 2 0 min-'.
Immediatelybefore the measurement, the cryo-particles
were mixed with an oil in an inert atmosphere and then
taken out and loaded onto the XRD-sample cell at ambient
conditions. The commonly accepted Scherrer formula was
used to calculate crystallite size from the diffraction peak
broadening. The zinc dust was used as an external standard.
The size of the zinc cryo-crystalliteswas determined to be
400-450 A, and the size of tin cryo-crystallites was more
than 2000 A.
For analysis of solid products from the reactions, several
consecutive isolation steps had to be performed. Floating
solids were collected by filtration on a fritted filter funnel
F. Then the liquid reaction mixture was shaken, causing
more flocculent material to rise in suspension while metal
particles again sank to the bottom. The suspended material
was decanted, filtered off, collected, and dried on the F
funnel. Lastly, the remaining, unreacted metal particles
were collected on another filter frit under ambient condi-
tions.
Calibration Curves. A series of blank experiments were
carried out: known amounts of COZ,CC4, or CHC13 were
injected into pure water in the reaction flask (injectedbelow
water level with stirring). Analyses of the headspace by GC
TABLE 1
Summary of Reactions Carried Out and Products
reaction. products found
CClp + Mg (ribbon) + H20 Mg(OH)2; Hz; CHC13 trace
CC14 + S n (mossy)+ H20 CHC13; COz; HCI;
SnOz (cassiterite)
CClp + S n (granular) + H20 t h e same; CO trace
CClp + Sn (cryo) + H20 t h e same; CHzCIz;
CIH2C-CH2CI trace
CC14 + Zn (dust) + H20 CHCI3; CH2C12; CH3CI; CHI;
ZnClz; Zn(0H)z; CO trace
CC14 + Z n (cryo, 360 A) + HzO t h e same; CIHzC-CH2CI
CHCl3 + Z n (dust) + H20 CH2C12; CH3CI; CH,; ZnCI2;
Zn(OH)2; CO trace
CH2CIz + Z n (dust) + H20 CH3CI; CHI; ZnCIz; Z n ( 0 H h
a 80-1OOpL of chlorocarbon and 8 x lo-* or 8 x mol of metal
in 100 mL of H20; under argon.
were carried out by extracting known volumes of gas and
injecting into the GC. A series of such control experiments
allowed construction of calibration curves that were used
to determine gaseous concentrations of COz, CCL, and
CHC13generated by the M/CC4/H20 reactions carried out.
Results
The reactions studied were usually carried out at room
temperature and are summarized in Table 1. Each metal/
CCL/HzO combination will now be described.
MglCCLIH20. Analysis of the gaseous headspace of the
reaction by FT-IR indicated the presence of CHC13and COz
in addition to HzO and CCL. Interestingly, the Mg ribbon
was transformed into a fine gray precipitate with the
evolution of bubbles of gas (Hz). After 48 h at room
temperature followed by heating for 2 h to about 40 "C, a
great deal of fine, white precipitate was formed, and the pH
of the solution was close to 10. Upon exposure of the
reaction mixture to air, the remaining gray solid (fine Mg
particles) was converted to more of the white precipitate
[Mg(OH)zI.
A blank experiment where no CC&was present indicated
that the Mg/HZO reaction took place to form Mg(0H)Zand
HZ,but at a slower rate, with the solution pH reaching about
8.
The conclusions from the experiments are that the
presence of CCL enhances the rate of the Mg/H20reaction,
yielding Mg(0H)Z and Hz more quickly. Only a small
amount of CCL was destroyed yielding CHC13.
Sn/CC4/H*O. All three samples of tin including granu-
lar, mossy, and cryo-particles caused the decomposition of
CCL over time. Chloroform, COZ,HCl, and solid SnOz
(cassiterite) were the products formed. In this case, the
pH of the solution went down to 1-2. The presence of C1-
in the aqueous solution was confirmed by precipitation
with silver nitrate.
Analysis of the headspace by GC, GUMS, and FT-IR
(Figure 1) confirmed that the major gaseous product was
CO2. The highly reactive cryo-particles caused the forma-
tion of CHzClz and CzH4C12 as well. Analysis of the aqueous
phase by GUMS also showed the presence of these same
products (COz,CHC13, CHzClz,and CzH4C1z).
In order to evaluate reaction rates, the headspace was
analyzed by GC with time. Chlorocarbon and COZcon-
centrations were calculated with the aid of a series of
calibration curves (see Experimental Section).
VOL. 29, NO. 6 , 1995 / ENVIRONMENTAL SCIENCE &TECHNOLOGY 1513
 co 0 012

il
I
100
n
A A CCI,
' E,
r
; 90
95

N
-
.
I
0010
A i
n
f 85
zj 0.008 A
IN
; 80
2 0006

'I ijl
0 0004
r CHCI,
2
4000 3500 3000 2500 2000
Uavenunbers
IS00

FIGURE 1. FT-IR of the headspace gas generated by the SnICCIJH20

1000
7
500
+ 0 002

reaction. Note the large COz band at 2348 cm-' and the absence 0,
0000
3. '
of the CHo band at 3013. CHCI,
I

1
6e-6 0 50 100 150 200 250 300
I

time, [min]
n 5e-6 FIGURE 3. Degradation of CC14 by different Sn patticles in water:
r, ( 0 )Sn (cryo); (A)Sn (granular). Curves drawn are simply to aid the

.
i
eye.

0.012
n
E,
n
N
., 0.010 t,71,
0008
IN
2 0006
i CH,CI,

5
0 0004
I
0 20 40 60 80 100 120 2 0 002
time, [hrs]
FIGURE2. Appearance of COZduring the SnICCIJH20 reaction. Molar
5
0 0.000
concentrations are given in exponential form. Curves drawn are
simply to aid the eye.
2
I , 1 I ,
Figure 2 compares the rate of C02 generated by tin 0 50 100 150 200 250 300
(granular vs mossy). Both the samples exhibited slow COz
generation over a 100-h period with granular Sn being the time, [min]
more active. In contrast, cryo-tinparticleswere much more FIGURE 4. Degradation of CC14 by Zn dust in water. Curves drawn
reactive (Figure 3) such that about 40% of the CC4 was are simply to aid the eye.
destroyed over a 3-h period. Both C02 and CHC13 were
generated much more quickly in the presence of cryo-tin, intermediate products such as CHC13 and CH2C12. For
and small amounts of CH2C12were also detected. example, in Figure 4, CC4 was degraded quickly, and the
Results with tin show that the surface area of the metal maximum CHC13 concentration occurred when about 20-
is very important for reactivity, and interestingly C02 is the 30% of the C C 4 remained. At that point, the degradation
major gaseous product. of CHC13began to exceed its production rate. After about
Zn/CC4/H20. Zinc proved to be the most promising 4 h, only a small amount of CCl, and CHC13 remained, and
metal, and so degradation of CC4 and CHC13 was studied 33-38% CHZC12 (percent of starting CC4) was observed.
over Zn dust and cryo-zinc particles. These results indicate that CH2Cl2 is of lower reactivitythan
Carbon tetrachloride degraded rather quickly, forming CCl4 and CHC13.
CHC13 and CH2C12. Eventually, these products were also When CHC13 was the starting material, it was almost
degraded and formed CHSC1, CH4, traces of CO, and zinc completely degraded in about 3 h, and by this time 60-
salts. Chloride ion was present in large amounts [ZnC12- 65% CH2C12 appeared. It was possible to follow this
(aq)], and Zn(OH12 formed as a very fine, white solid (as apparent stepwise degradation of CCb by FT-IR. In Figures
identified by XRD). Figures 4 and 5 show degradation 6 and 7, a series of spectra show the disappearance of CC4
patterns for CC14 and CHC13with time. and the gradual appearance of CH4. The spectra also
Gaseous products were identified by a variety of suggest the appearance and then the disappearance of
methods: CH3Clby GUMS, CO by FT-IR, and CH4 by GC CHC13 along with CH2Cb appearance (CH3Cl could not be
and FT-IR. It was possible to observe the appearance of observed by this method). In particular the following

1514 rn ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 29, NO. 6. 1995

 CHC'3 CCI,
0.014
.,
.I
5 0,012
c,
5 C
0.010
Q
2 0.008
0

8 0,006
5
I" 0.004
0
'0 0.002
c
0
0.000
CH,CI,
3
0 20 40 60 80 100 120 140 160 180 200 220

time, [min]
FIGURE 5. Degradation of CHC13 by Zn dust in water. Curves drawn
are simply to aid the eye. w 22.5 hr

w I'

3000 2200 I400 600

W A V E N U M B E R S (cm")
f 601
FIGURE 7. FT-IR of the headspace gas generated by the ZnICCIJHzO

'1
reaction with time. Note progressive appearance/disappearance
of CHCIJ, CHZCII, and CH4.
10

1"
*- I
1 I I I 1 I
40W BW 3000 2600 2opO 1500 IOW
Ulvarmlbare
FIGURE 6. FT-IR of the headspace gas generated by a long-term (27
h) reaction of ZnICCIJHZO. Note the absence of COZ(2348cm-') and
the large amount of CHI (3013 cm-'1.
adsorptionscould be monitored in this way CCL 773 cm-l;
CHC13, 1215 cm-l; COZ,2348 and 666 cm-l; H20, 1250-
2000 cm-'; CH2C12,1262-1279 and 746 cm-I; and CH4,
3013 and 1303-1342 cm-'. The CCh and CHC13 bands
essentially disappeared while CH2C12and CH4 remained.
In additional experiments, it was shown that CH2C12
degradation was slower than CCL and CHC13 (Figure 8).
This results suggest a sequential degradation process.
The rates of degradation of these compounds were quite
dependent on metal surface area (Figure 9). Thus, 5 g of
Zn dust caused much more rapid degradation than 1 g and
also shortened the induction time before the onset of
product formation.
Cryo-zinc particles gave the best results (Figure 9).
Extremely high reactivity was observed initially, and after
about 1 h the rate of CC4 degradation slowed down
somewhat.
Discussion
Choice of Metal and Metal Morphology. The data clearly
show that the choice of metal is very important. As might
be expected, high surface area is beneficial. In addition,
nanocrystalline, high surface area metal particles are best,
I and these observations are also not surprising considering
600
the substantial body ofliterature published on the chemistry
of "activated metals" (13,141. However, what is particularly
intriguing,regarding the use of such metal particles in
aqueous media is that a balance must be struck between
reactivity with water vs chlorocarbon. In the case of Mg,
oxidation of the metal by water tends to defeat its high
reactivity with the chlorocarbon. Therefore, tin and zinc
appear to be better choices since their reactivitywith water
is lower, and yet they still are sufficiently reactive with the
chlorocarbons.
Of course, the chemistry involved is complex. Metal
hydroxide andlor oxide that forms on the surface of the
metal tends to protect it from further water oxidation. In
the best scenario, the chlorocarbon would still be capable
of attacking the metal even in the presence of this protective
hydroxideloxide coating. These considerations suggest that
kinetic parameters will be the controlling features.
On the other hand, perhaps thermodynamics can aid in
at least making rough predictions of reactivity and selectiv-
ity. Table 2 lists a few AHf" values for metal chlorides and
metal hydroxides. As was pointed out in the Introduction,
perhaps more favorable AHfo for the metal chlorides is
important. Thus, if there is any validity to this type of
comparison, it might be predicted that Mg, Ca, Fe, Ni, Zn,
Cd, and Pb could possibly react with CCb competitively
with water. However, to carry this argument further, the
AH," for CC4 and H20 should be compared for reactions

VOL. 29, NO. 6 , 1 9 9 5 /ENVIRONMENTAL SCIENCE &TECHNOLOGY 1515

 0.012

-
E,
0010
Zn(dust,lg)

c" 0008 ' e

.
0
I
c1
5
Y
C
0.006 + 'Zn(dust,Sg)
A

Q,
0.004 i
8
-* 0,002
0
0
0.000

I 0 50 100 150 200 250

time, [min]
FIGURE 9. Degradation of CCI, by Zn patticles of different surface
areas due to the amount of Zn dust added and the use of cryo-zinc.
Curves drawn are simply to aid the eye.

TABLE 2
Standard Heats of Fonnation of Selected Metal
Chlorides and Oxide9
difference
3000 2200 1400 600 A/-( chloride (kJ/mol) A$ oxide (kJ/mol) (chloride - oxide)

w A v E N u M B E R S (an-') Mg -641 -602 -39

Ca -795 -635' -160
FIGURE 8. FT-IR of the headspace gas generated by the Zn/CH2- Ti -804 (Tic141 -944 (Ti021 $140
CI/H20 reaction with time. Note the disappearance of CHZCIZand -514 (TiC12) -519 (TiO) +5
the appearance of CH4. Cr -557 (CrC13) - 1 140 0 2 0 3 ) +I3
Fe -400 (FeC13) -824 (Fez031 +12c
such as 4-6. Of course, reaction 4 would not occur in -342 (FeC12) -272 (FeO) -70

+ CC1,(1) - 2ZnClz(s) + C(s)

Ni -305 (NiC12) -489 (Ni203) -60'
2Zn(s) (4) CU -137 (CUCI) -169 (CUZO) - 53c
-220 (CuCI2) -303 (CUO) $83
Zn(s) + H,O(l) - ZnO(s) + H,(g)
Zn -415 -351 -64
, (5) Cd -392 -258d -134

-
Zn(s) + 2Hz0(1) Zn(OH)(s) + H,(g) (6)
Ge
Sn
-532
-511 (SnC14)
-325 (SnC12)
-580
-577 (Sn02)
-281 (SnO)
+48
+66
-44
Pb -359 (PbC12) -217 (PbO) -142
water, but it could be used to evaluate the exothermicity
a Linde, D. R., Ed.; CRC Handbook of Chemistry and Physics, 75th
of ZnClz formation. This really comes down to looking at ed., CRC Press: Boca Raton, FL, 1994; pp 5-4-5-30. Ca(OH)2 AHfo =
the difference in AHf" of the metal chlorides minus AHp- -985 kJ/mol. AHf"for Cr203/2 = -570; for Fez03/2 = -412; for Ni203/2
(CC&) and the metal oxides minus AHfo(H,O),and so the = -245; for Cu20/2 = -84.5. Cd(OH)2AHf' = -561.
trends from Table 2 would not change. What would be
formation with time. Therefore, it seems reasonable to
more helpful would be to look at AHf" of the hydroxides,
but few of these are reported in the literature. It seems propose a multistep reduction sequence as shown in Figure
10. Here, CCl, oxidatively adds to Zn forming C13CZnC1, a
pointless to try to carry these considerations further until
reactive intermediate that would be susceptible to rapid
complete product analyses can be carried out and ther-
modynamics of aqueous species can be considered. protonation by water. In a similar way, CHC13,CH2C12,and
Dominant Chemical Reactions. Perhaps the most CH3Cl could be attacked and protonated. Overall, a
striking finding from this work is that the chemistry of the balanced equation for complete reaction could be written
MICC14IH20 system can change dramatically depending as follows:
on the metal. The two metallic elements that were 4Zn(s) + CC1,(1) + 4H20(1)- ZZnCl,(aq) +
successful in degrading CCl, over time were Sn and Zn. 2Zn(OH),(s) + CH,(g)
However, the dominantfinal product in the case of SnICCld
H 2 0 was CO2, while the dominant final product in the case Note that no HC1 is formed according to this equation. This
of ZnICC1dH20 was CH,. Obviously, these products are seems reasonable since the pH of the solution did not fall
"complete opposites" in terms of oxidation vs reduction. very much (pH - 6 after reaction). Also, the formation of
How can this be rationalized? ZnC12(aq) would explain the copious amounts of C1-
With Zn, the stepwise production of CHCl3, CHZC12, and precipitated by the addition of AgN03. Zn(OH12 was also
eventually CHI was rather evident by following product found as a solid, fine precipitate.

1516 a ENVIRONMENTAL SCIENCE &TECHNOLOGY / VOL. 29, NO. 6, 1995

 M + CC14 - C13CMCI
C13C-H +
“Y
HOMCI
\
C12C: + MCI2
IM
1 t
H CI
C12C-M-CI MO;MC12 I chlorocarbons depends on the quantity of the metal and
I (cryo-particles).
H
CI
1 (cryo-particles) allowed the shortest induction time and
‘.C=O + HCI
i
b l
CHA
_. -7
C02 + 2 HCI
I The partial support of the National Science Foundation
FIGURE 10. Proposed reaction intermediates in the M/CCIdhO
reactions (where M = Zn, Sn) that help explain product differences
with Zn and Sn.
With Sn, a similar reaction could begin the sequence
(Figure 10). Oxidative addition of CC& to Sn could yield
C13CSnC1. This species would also be somewhat susceptible
to protonation by water, but it would be expected that this
would be less favorable since Sn-Cl bonds are less ionic
than Zn-C1 bonds.
If the protonation of C13CSnC1is slower,then an expected
decomposition pathway might dominate, that of CC12
elimination. If this happened the reaction of CClp with
water would be expected to beveryfast, forming anunstable
alcohol that would eliminate HCl and ClZCO (phosgene)
(15). However, phosgene would be susceptibleto hydrolysis
by excess water in the same way that other organic acyl
chlorides are. The final products would indeed be COZ
and more HC1.
An overall balanced equation might be written as follows:
+ CC1,(1) + 4H20(1)- Sn02(s)+ 4HCl(aq) +
Sn(s)
Cop(@ + 2H2(@
This reaction is supported by the observation of SnOz and
Copand the development of low pH (between 1 and 2 after
reaction). We have not yet confirmed the presence of
hydrogen. Of course, these balanced equations are ide-
alistic. In the tin system, small amounts of CHC13 and CH2-
Clz were also observed, and occasionally two carbon
products such as C2H4ClZ were also detected.
Although a complete mass balance study remains to be
completed and it is possible that other (undetected)
products exist, it seems that the formation of C13CMC1 as
an initial reactive intermediate is a reasonable working
hypothesis. The competition between protonation by water
or elimination of CCh can be used to rationalize product
mixtures observed. Further work may delineate if other
reaction pathways exist, for example, electron transfer
processes involving radical anion intermediates.
Conclusions
(1) Sn (mossy, granular, cryo-particles) causes the degrada-
tion of CC&in water solutions with CHC13, Sn02,CO2, and
HCl as the main products.
(2) Zn (dust, cryo-particles) is more reactive than Sn
and causes the degradation of CC&,CHC13, and CHpClp in
water solutions. The final products are CH3C1, CH4, ZnCh
and Zn(OH)2.
(3) The different products found in the Sn and Zn
reactions possibly indicate different mechanisms of the
chlorocarbon degradation.
(4)The ability of Zn and Sn particles to decompose the
its surface properties and increases in the order: Sn (mossy)
< Sn (granular) < Sn (cryo-particles) < Zn (dust) < Zn
(5) The metal particles obtained by the SMAD method
the most rapid degradation of chlorocarbons.
Acknowledgments
and the Army Research Office is acknowledged with
gratitude. Partial support of the Hazardous Substance
Research Center (through the U.S. Environmental Protec-
tion Agency under Assistance Agreement R-815709 to
Kansas State University) is also acknowledged.
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Received for review August 3, 1994. Revised manuscript re-
ceived February 23, 1995. Accepted March 6, 1995.@
ES940492D
@Abstractpublished in Advance ACS Abstracts, April 15, 1995.
VOL. 29. NO. 6,1995 / ENVIRONMENTAL SCIENCE &TECHNOLOGY 1517