Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
Supplementary information for
Photoaccelerated oxidation of chlorinated phenols
Gábor Lentea and James H. Espenson*b
a
Department of Inorganic and Analytical Chemistry, University of Debrecen, Debrecen,
Hungary. Fax: 36-52-489-667; Tel: 36-52-512-900; E-mail: lenteg@delfin.klte.hu
b
Ames Laboratory, Iowa State University, Ames, IA, USA. Fax: 1-515-294-5233; Tel: 1515-294-5370; E-mail: espenson@ameslab.gov
Experimental information:
Chlorinated phenols purchased from Aldrich and Lancaster Synthesis were purified by
vacuum sublimation. The iron complexes used as catalysts were prepared using published
methods except iron(III) meso-tetra(4-sulfonatophenyl) porphine chloride, which was
purchased from Frontier Scientific (www.porphyrin.com).
Shimadzu UV-2501PC (scanning), UV-3101PC (scanning), MultiSpec-1500 (diodearray) spectrophotometers and a Shimadzu TOC-5000A total organic carbon analyzer
were used in this study. NMR spectra were recorded on a Varian VRX-300 and a Bruker
DRX-400 instrument. NMR spectra were calibrated using the residual signal of the
solvent. A Weiss Research CL3005 combination chloride ion selective electrode and a
Hanna Instruments HI 1131 combination pH electrode were used attached to a Hanna
Instruments pH302 pH-meter. The electrodes were calibrated every day using standard
NaCl solutions and standard buffers, respectively. The response function of the chloride
ion selective electrode showed a very reproducible curvature at low chloride ion
concentrations. Our observations on this curvature were in excellent agreement with the
specifications provided by the manufacturer of the electrode, and a parabolic calibration
was used in the nonlinear region. Kinetic experiments with the chloride ion selective
electrode were always carried out with a small amount of NaCl added prior to the
experiment (referred to as [Cl-]0 in the figure captions or figures) in order to avoid badly
defined voltage readings at the beginning of the curves. The lamp used in this study was a
commercially available Regent 500 Watt Halogen Worklight (Regent Lightning
Corporation, Burlington, NC, USA). The spectral properties of the lamp were recorded
by directing its light beam to the detector of a diode-array spectrophotometer.
1
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
b
c
0.4
a
A
d
e
0.2
0.0
270
280
 (nm)
290
300
Fig. S1 Spectral changes in the reaction of TCP with H2O2 in the absence of a catalyst. a:
freshly prepared reaction mixture; b: after 6 days in the dark; c: after 18 days in the dark;
d: after 6 days in room light; e: after 18 days in room light. [TCP] = 1.95 mM; [H2O2] =
90 mM; T = 25.0°C; 1 mm cell.
0.08
0.04
0.00
200
400
 (nm)
600
2
bitrary)
Fig. S2 Spectral characteristics of the halogen worklight used in this study.
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry
0.1 M2003
NaNO
3
300
E (mV)
200
100
-5.0
-4.0
-3.0
log [Cl - ]/M
-2.0
Fig. S3 Calibration curve for the chloride ion selective electrode.  = 0.1 M (NaNO3); T
= 25.0°C.
lamp turned on
] (mM)
0.7
[Cl
-
1.4
0.0
0
30
t (min)
60
Fig. S4 Effect of light on the oxidation of TCP by H2O2 catalyzed by hexaaquairon(III).
[Fe(III)] = 0.18 mM; [TCP] = 1.51 mM; [Cl-]0 = 5.0 M; [H2O2] = 97 mM;  = 0.1 M
3
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
(NaNO3); T = 25.0°C.
4
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
0.3
lamp turned on
-
0.2
0.0
] (mM)
[Cl
0.1
[Cl - ]
0
0
40
t (min)
80
Fig. S5 Effect of light on the oxidation of TCP by H2O2 catalyzed by iron
tetrasulfophthalocyanine. [catalyst] = 7.0 M; [TCP] = 1.51 mM; [Cl-]0 = 0.10 mM;
[H2O2] = 97 mM;  = 0.1 M (NaNO3); T = 25.0°C.
5
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
0.0
0
] (mM)
0.7
[Cl
-
1.4
lamp turned on
30
t (min)
60
Fig. S6 Effect of light on the oxidation of TCP by H2O2 catalyzed by Fe(TPA)2+.
[Fe(TPA)2+] = 0.11 mM; [TCP] = 1.61 mM; [Cl-]0 = 5.0 M; [H2O2] = 97 mM;  = 0.1 M
(NaNO3); T = 25.0°C.
6
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
1.4
lamp turned off
0.0
] (mM)
0.7
[Cl
-
lamp turned on
[Cl - ]
0
0
40
t (min)
80
Fig. S7 Effect of light on the oxidation of TCP by H2O2 catalyzed by cis-Fe(cyclam)3+.
[cis-Fe(cyclam)3+] = 0.13 mM; [TCP] = 1.61 mM; [Cl-]0 = 0.57 mM; [H2O2] = 97 mM; 
= 0.1 M (NaNO3); T = 25.0°C.
lamp turned off
lamp turned on
0.05
0.00
0
[Cl - ]
] (mM)
[Cl
-
0.10
0
15
t (min)
30
Fig. S8 Effect of light on the oxidation of 2,6-dichlorophenol by H2O2 catalyzed by
Fe(TPPS)+. [Fe(TPPS)+] = 2.9 M; [2,6-dichlorophenol] = 0.85 mM; [Cl-]0 = 0.048 mM;
7
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
[H2O2] = 46 mM;  = 0.1 M (NaNO3); T = 25.0°C.
8
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
0.3
lamp turned on
[Cl
0.1
] (mM)
-
0.2
-
[Cl ]0
0.0
0
50
t (min)
100
Fig. S9 Effect of light on the oxidation of 2,4-dichlorophenol by H2O2 catalyzed by
Fe(TPPS)+. [Fe(TPPS)+] = 3.1 M; [2,4-dichlorophenol] = 1.34 mM; [Cl-]0 = 0.1 mM;
[H2O2] = 97 mM;  = 0.1 M (NaNO3); T = 25.0°C.
9
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
0.3
lamp turned on
0.2
0.1
0.0
0
] (mM)
[Cl
-
[Cl - ]0
20
t (min)
40
Fig. S10 Effect of light on the oxidation of 2,4,5-trichlorophenol by H2O2 catalyzed by
Fe(TPPS)+. [Fe(TPPS)+] = 2.9 M; [2,4,5-trichlorophenol] = 0.73 mM; [Cl-]0 = 0.20 mM;
[H2O2] = 46 mM;  = 0.1 M (NaNO3); T = 25.0°C.
10
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
[Cl
0.2
0.0
0
] (mM)
-
0.4
lamp turned on
-
[Cl ]0
15
t (min)
30
Fig. S11 Effect of light on the oxidation of 2,3,4,6-tetrachlorophenol by H2O2 catalyzed
by Fe(TPPS)+. [Fe(TPPS)+] = 2.9 M; [2,3,4,6-tetrachlorophenol] = 0.32 mM; [Cl-]0 =
0.12 mM; [H2O2] = 46 mM;  = 0.1 M (NaNO3); T = 25.0°C.
11
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
0.2
[Cl
0.1
0.0
] (mM)
-
lamp turned on
[Cl - ]0
0
50
t (min)
100
Fig. S12 Effect of light on the oxidation of 2,6-dichloro-1,4-benzoquinone by H2O2
catalyzed by Fe(TPPS)+. [Fe(TPPS)+] = 3.1 M; [2,6-dichloro-1,4-benzoquinone] = 0.34
mM; [Cl-]0 = 20 M; [H2O2] = 97 mM;  = 0.1 M (NaNO3); T = 25.0°C.
12
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
0.0
0
] (mM)
lamp turned on
0.2
[Cl
-
0.4
[Cl - ]0
40
t (min)
80
Fig. S13 Effect of light on the oxidation of 2,6-dichlorohydroquinone by H2O2 catalyzed
by Fe(TPPS)+. [Fe(TPPS)+] = 3.1 M; [2,6-dichlorohydroquinone] = 1.61 mM; [Cl-]0 =
20 M; [H2O2] = 97 mM;  = 0.1 M (NaNO3); T = 25.0°C.
13
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
1.8
d
A
1.2
0.6
0.0
300
c
a, b
400
500
 (nm)
600
700
Fig. S14 Uv-vis spectral changes in the aqueous photoreaction of 2,6-dichloro-1,4benzoquinone. a: freshly prepared solution, b: after 70 minutes in the dark, c: after 65
minutes in room light; d: after 61 minutes of illumination. [2,6-dichloro-1,4benzoquinone] = 2.2 mM; T = 25.0°C; 1 cm cell.
14
Supplementary material (ESI) for Chemical Communications
This journal is © The Royal Society of Chemistry 2003
-
2.0
0.0
lamp turned on
] (mM)
[Cl
1.0
[Cl - ]0
0
15
t (min)
30
Fig. S15 Effect of light on the oxidation of TCP by KHSO5 catalyzed by Fe(TPPS)+.
[Fe(TPPS)+] = 3.1 M; [TCP] = 1.80 mM; [Cl-]0 = 50 M; [KHSO5] = 101 mM;  = 0.28
M (KHSO5/KHSO4/K2SO4); T = 25.0°C. The decreasing part between 5 min and 15 min
most likely corresponds to some oxidation of Cl- by HSO5-, which is known to be a
thermodynamically allowed reaction.
15