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USE OF A KINETIC MODEL TO UNDERSTAND
THE EFFECT OF IRON(II) AND BICARBONATE
ON THE OZONATION OF 1,2-DICHLOROBENZENE

By

Ming-Kuei Chiang

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Civil and Environmental Engineering

1993

ABSTRACT

USE OF A KINETIC MODEL TO UNDERSTAND
THE EFFECT OF IRON(II) AND BICARBONATE
ON TEH OZONATION OF 1,2-DICHLOROBENZENE

BY

Ming-Kuei Chiang

This study was conducted to investigate the effects of
bicarbonate and ferrous iron on 1,2-dichlorobenzene oxidation
using ozonation processes. A.kinetic model was also developed
to simulate experiments.

In the oxidation processes, the 1,2-dichlorobenzene
removal efficiency was decreased and the ozone consumption was
increased when the concentration of bicarbonate was increased
from 0.002 M to 0.005 M. Thus, the effect of bicarbonate
cannot be explained only the scavenging of the hydroxyl
radicals which should decrease both 1,2-dichlorobenzene
removal and ozone consumption. However, an additional
explanation for the effect bicarbonate is the reaction of°C05
radical with ozone which consumes excess ozone.

The role of Fe“’acting as an initiator or a scavenger in
ozonation treatment systems depends (n1 the ozonation
condition. At neutral pH, the reaction of Fe2+ initiating
ozone decomposition is a dominant in ozone treatment, but the
reaction of Fe“’scavenging hydroxyl radicals is the dominant

reaction in O3/UV and O3/H202 treatments.

A model developed by using acuchem program shows a good
agreement with the experimental results for O3, O3/UV, and

O3/H202 treatment systems at the pH range S~8.

ACKNOWLEDGMENTS

I would like to extend my appreciation to Dr. Susan J.
Masten and Dr. Simon Davies for their professional guidance
and advice.

I also wish to thank C. C. David Yao for supplying

Acuchem computer program.

iv

TABLE OF CONTENTS

LIST OF TABLES ....... ............. ............... . ...... Vii
LIST OF FIGURES ..... . ..... . ................. .... ........ 1X
0

CHAPTER 1 INTRODUCTION

G EN ERAL O O I O O O ..... O O O O O I O O O O O O i O O O O O O O O I O ..... O O O O O O 1
OBJECTIVES . .................... . ..... . ...... ....... 3
BACKGROUND 0 ..... O O O O O O O 00000000000000 O ........ O O O O O 3

CHAPTER 2 MATERIALS AND METHODS

SYSTEM CONFIGURATION .............. ................. 11
REAGENTS ......................... ................. . l4
ANALYTICAL METHODS ......................... ........ 15
EXPERIMENTAL PROCEDURE ............................. 16

CHAPTER 3 KINETIC MODEL
THEMODELMECI'IANISMS 00......CCOCOOOOOOCOOOOOOOOOOOO 20

MODEL MODIFICATION FOR CONTINUOUS FLOW SYSTEM ...... 26

CHAPTER 4 RESULTS AND DISCUSSIONS .... ..... ............. 29

CHAPTER 5 CONCLUSIONS

CONCLUSIONS 0 O O I O O O O O O O O O O 000000000000 O O ...... O O O O O O 44

FUTURE REstCH O O O O O ...... O O ..... O C 0000000000000 C O O 46
REFERENCES ......... ..... ....... . ..................... ... 47
APPENDICES

APPENDIX A The Kinetic Model of Ozonation Processes
for ACUCHEM Computer Program ........... 51

APPENDIX B The Results of Kinetic Model Simulation

O......OOOOOOOOOOOOO......OOOOOOOIOOOOOO 55

APPENDIX c Ozone, DCB, 3202, and Fe“ Sampling Summary
for Each Experiment .................... 61

vi

Table

Table
Table

Table

Table

Table

Table

Table

Table

Table
Table

Table

Table

Table

Table

1.1

2.1

2.2

2.3

3.1

3.2

4.1

4.2

4.3

4.4

4.5

4.6

4.7

4.8

8.1

LIST OF TABLES

Oxidation-Reduction Potentials of Water
Treatment Agents ..................... ........

The List of Experimental Apparatus .. ....... ..
The List of Experiments in This Study ........

The.0peration.Condition for Equipments in each
system OO.........OOOOOOOOCOOOOOOO00.0.0000...

A List of Reactions and Rate Constants Used in
the KinetiCMOdel 0..........OOOOOOOOOOOOOOOOO

The Estimation of Rate Constants for Reactions
R3 and R5 ....00.0.0.........OOOOOOOOOOOOOOOOO

Degradation Rate of DCB, O3, and Fe“ in
Ozone Treatment ...................... ....... .

Degradation Rate of DCB, 03, and Fe“ in
Ozone/UV Treatment ...........................

Degradation Rate of DCB, 03, H202, and Fe2+ in
Ozone/th Treatment ..........................

The Effect of HCO; on DCB Removal Efficiency..
The Effect of HCOg on 03 Degradation Rate ....

The Effect of Fe2+ on DCB and 03 Degradation
Rate at pH6......C.........OOOCOOOOOOCOOCOOO

The Estimation of the Rate Constant for FeiW/O3
Reaction .0.........C...................000...

The % Difference Between Model Simulations and
Experimental Results at Neutral pH ...........

The Input/Output Data of Kinetic Model for
Ozone Treatment System .......................

vii

1
13

17
18
21
25
30
31

32

35
37
41.
42

55

Table

Table
Table

Table

Table

Table

Table

Table

Table

Table
Table

Table

Table

Table

Table

4.8

B01

LIST OF TABLES

Oxidation-Reduction Potentials of Water
Treatment Agents ...................... .......

The List of Experimental Apparatus .. .........
The List of Experiments in This Study ........

The Operation Condition for Equipments in each
system O......OOIOOOOOOO0.0.0.000... ........ O.

A.List of Reactions and.Rate Constants Used in
the Kinetic Model ............................

The Estimation of Rate Constants for Reactions
R3 andRS I.........IOOOOOCOOOOOOOO0.0.0.0....

Degradation Rate of DCB, O3, and Fe2+ in
ozone Treatment ......C.......................

Degradation Rate of DCB, O3, and Fe2+ in
ozone/WTreatment ...-......C................

Degradation Rate of DCB, O3, H202, and Fe2+ in
Ozone/Hg» Treatment ..........................

The Effect of HCO; on DCB Removal Efficiency..
The Effect of HCO; on O3 Degradation Rate ....

The Effect of Fe2+ on DCB and O3 Degradation
Rate at pH60.0.0..........OCOOCCCCCOOOCOCOOO

The Estimation of the Rate Constant for Fe“/O3
Reaction .........OOOOOOOOOOOOO...00.0.0000...

The % Difference Between Model Simulations and
Experimental Results at Neutral pH ...........

The Input/Output Data of Kinetic Model for
Ozone Treatment System .......................

vii

1
13

17
18
21
25
30
31

32

35
37
41.
42

55

Table 8.2 The Input/Output Data of Kinetic Model for
Ozone/UV Treatment System .................... 57

Table 3.3 The Input/Output Data of Kinetic Model for
Ozone/H45 Treatment System ................... 59

viii

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

Figure

LIST OF FIGURES

1.1 The Decomposition of Ozone in Pure Water .... 4
1.2 The Decomposition of Ozone Containing
Reactant Species ............................ 7
2.1 The Experimental Configuration of Ozonation
system 0....0.0.0..........OOOOOOOOOOOOOOOOOO 12
4.1 Effect of Bicarbonate Concentration on DCB
Removal Efficiency in Ozone Treatment System
..................OOOOOOCCOOOOCOOO0.0.0.0.... 33
4.2 Effect of Bicarbonate Concentration on DCB
Removal Efficiency in Ozone/UV Treatment System
......OOOOOO......O...00.00.00.000...00...... 33
4.3 Effect of Bicarbonate Concentration on DCB
Removal Efficiency in Ozone/H55 Treatment System
0.000.000.0000.0............OOOOOOOOOOOOOOOOO 33
4.4 Effect of Bicarbonate Concentration on Ozone
Consumption in Ozone Treatment System ....... 34
4.5 Effect of Bicarbonate Concentration on Ozone
Consumption in Ozone/UV Treatment System .... 34
4.6 Effect of Bicarbonate Concentration on Ozone
Consumption in Ozone/H45 Treatment System ... 34
4.7 Effect of Fe(II) on DCB Removal Efficiency in
Ozone Treatment System ...................... 38
4.8 Effect of Fe(II) on DCB Removal Efficiency in
Ozone/UV Treatment System ................... 38
4.9 Effect of Fe(II) on DCB Removal Efficiency in
Ozone/H45 Treatment System .................. 38
4.10 Effect of Fe(II) on Ozone Consumption in
Ozone Treatment System ...................... 39

ix

Figure 4.11 Effect of Fe(II) on Ozone Consumption in
Ozone/UV Treatment System ................... 39

Figure 4.12 Effect of Fe(II) on Ozone Consumption in
ozone/H202 Treatment system a o o o o o o o o o o o o ooooo 39

CHAPTER 1

INTRODUCTION

GENERAL

Ozone is a very powerful oxidant (E0 = 2.07 volts in
alkaline solution), which is capable of reacting with numerous
organic chemicals. It is more powerful than most of other
oxidants currently used in water treatment (see Table 1.1).
However, many organic matters (e.g., aliphatic amines) only
react slowly with molecular ozone. For these matters, the

processes involving the 'OH radical generation may provide more

Table 1.1 Oxidation-Reduction Potentials
of Water Treatment Agents

 

 

Reactions Potential in Volts (EU) at 25 uC
F, + 2e‘ = 2F‘ 2.87
o, + 211* + 2e’ = 02 + H20 2.07
H202 + 2H” + 2e‘ = 21120 (acid) 1.76
mm; + an + 3e’ = 1411102 + 2320 1.68
Hc102 + 311* + 4e‘ = or + 211,0 1.57
HOCl + H” + 2e' = C1’ + H20 1.49
c12 + 2e‘ = 2c1' 1.36
HOBr + H+ + 2e’ = Br‘ + H20 1-33
Brz + 2e' = ZBr' 1-07
c102,“, + e' = C10; 0-95
11,02 + 2H3O+ + 2e' = 411,0 (base) 0-87

 

* Ozone Treatment of Industrial Wastewater, 1981. Noyes Data
Corporation, New Jersey, p 17. '

effective treatment.

The OR radical is an extremely strong and non-selective
oxidant (E0 = 3.06 volts). The processes resulting in the
formation of 'OH radicals in sufficient quantity to affect
water treatment are referred to as advanced oxidation
processes (AOPs) . These processes include ozone in combination
with UV irradiation, ozone with added hydrogen peroxide,
hydrogen peroxide in combination with Fe(II), hydrogen
peroxide with UV irradiation, etc.. The processes of ozone in
combination with UV irradiation (O3/UV) and ozone with added
hydrogen peroxide (O3/H202) were the two AOPs studied in this
work.

The application of ozone for the disinfection in water
treatment began in Nice, France in 1907. By the 1960's, ozone
was also used for odor control in wastewater treatment.
Although the ozonation has been widely used in water and
wastewater treatment facilities and more and more successful
applications have been reported, these remain a lack of
knowledgement of the mechanisms by which ozone decomposes. The
lack of understanding the complex reactions of natural organic
matter in aqueous ozone systems will become a major obstacle
for further ozone applications.

In recent years, many possible reaction sequences in
aqueous ozone solution were published (e.g., Btihler et al.
1984, Holcman et al. 1982, Gary et al. 1988, Sehested et al.
1982, 1984, 1991, Staehelin et al. 1982, 1984, 1985 ...). The

mechanisms for ozone decomposition developed by Staehelin,

3
Bfihler and Hoigné (SBH) are widely accepted although some of
reactions are in dispute (e.g., the existence of 1H»). This
mechanism is considered the most reliable system for ozone

decomposition in pure water.

OBJECTIVES

In previous investigations, 1,3,5-trichlorobenzene and
1,2-dichlorobenzene have been studied in aqueous systems by
using ozone, ozone/UV, and ozone/H55 treatments at various pH
and portions of these studies have been published (Masten
et al., 1993). Based upon the results of these series of
investigations, the ‘major’ objectives of ‘this study ‘were
formulated to be (1) to investigate the effect of ferrous ion
or/and bicarbonate ion on the efficiency of treatment of
1,2-DCB with advanced oxidative processes and (2) to develop
a numerical model to describe the kinetics of oxidation and

the efficiency of treatment processes.

BACKGROUND

The pathways of the ozonation for organic matters are:
(1) direct attack by molecular ozone via cycle-addition or
electrophilic reaction, and (ii) indirect attack by free
radicals (primarily 'OH) produced by the decomposition of
ozone. In aromatic compounds, the ozonation of the compounds
substituted with electron-donating groups (e.g., -OH or -NHQ
is faster than it of the compounds substituted.with electron-

withdrawing groups (e.g.,-duh, -Cl, -COOH). Hoigné and Bader

H4-

 

03 )

()H' '
KC()2. z H02 ()2

{030m

 

 

 

02

Figure 1.1 The decomposition of ozone in pure water
(Adapted from Staehelin and Hoigne. 1985)

5

(1983) determined the rate constants of the reaction of ozone
with substituted benzenes, phenol > toluene > benzene >
chlorobenzene > nitrobenzene. Generally, the more chlorinated
compound is more difficult to be oxidized.

Ozone decomposition is a complex succession of reactions.
It has been extensively studied (e.g., Sehested et al. 1982,
1984, 1991, Staehelin et al. 1982, 1984, 1985). Staehelin
et al. have proposed a series of mechanisms that are widely
accepted as a basic model for ozone decomposition in pure
water (see Figure 1.1). The elementary steps of ozone

decomposition are listed as follows :

Initiation :
03 +03 --v'02‘+°H02 (1)
( °H02 «--—» 02' + H“ )

Propagation :
-o,- + 03 --—wo,' + 02 ..... (2)
‘03’+H+ ...—.1103 .. ..... (3)
1103 -—. 01-14-02 ............ (4)
(”1+03 ...... 1.104 ............ (5)
1.104 -... 1102+ 02 (6)
'H02 ......02-+H+ (7)

The decomposition of ozone in pure water is initiated by
reaction (1) . Ozone (03) reacts with hydroxide ion (OH‘) to
produce superoxide anion ('02') and hydroperoxyl radical ('HOZ) .
The chain propagation reactions: the transfer of an electron

from '02‘ to 03 forms the ozonide ion ('03') with the release of

6

O2 (reaction 2); the protonation of '03‘ to form 110, followed by
the decomposition of THE to produce a hydroxyl radical (OH)
with the release another 02 molecule (reaction 3,4); the
reaction of 'OH and 03 forms a charge-transfer complex (110,)
which decays into 'HO, and O2 (reaction 5,6); the decomposition
of 'H02 forms '02' and H+ (reaction 7). The “02' enters the first
step of the cyclic reactions shown in Figure 1.1. In the
propagation step, '02' and '01! are both chain carriers which
promote the cyclic reactions. Although some mechanisms of this
model are still in dispute (ex. the existence of TE»). It is
the most reliable mechanism for ozone decomposition in pure
water.

"Real" water systems contain many organic solutes or
other impurities such as humic acid, carbonate species, iron,
aromatic compounds, etc.. The ‘mechanisms by ‘which ‘these
solutes are involved in ozone decomposition are much more
complex than that of which occurs in pure water. The solutes
may act as initiators, promoters, or inhibitors in ozone
decomposition or consume ozone only because of the direct
reaction of the molecule with ozone (see Figure 1.2).
Initiators react with ozone and form 'O,’ via an electron
transfer reaction. Promoters are capable of regenerating 15’
by free radical reactions. Inhibitors scavenge free radicals
such as on radicals resulting the decrease of°Oi formation.

Ferrous ion (Fe“) is a common metal ion that exists in
ground water at concentration greater than 0.3 mg/L. In

aqueous ozone systems, it has been proposed that ferrous ion

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Figure 1.2 The decomposition of ozone containing reactant species.
M is a pollutant which reacts with ozone directly
I is an initiator which reacts with ozone to initiate the chain reaction
P is a promoter which reacts with “OH to form a radical species
S is a scavenger which reacts with 'OH to terminate the chain reaction

8

reacts with ozone by an electron-transfer reaction and forms
an ozonide ion (Hart et al., 1983), i.e. Fe2+ acts as an
initiator. Protonation of ‘03' results the formation of the
hydroxyl radical. Thus, the net reaction is:

Fe2++ 03+ H+-->Fe3++ 02+ on . . . . . . . . . . . . (8)
If there is excess Fe“) the OH radical would oxidize a second
Fe“'(reaction 9).

Fe2+ + on --» Fe3+ + on' (9)
Nowell and Hoigné (1987) suggested an alternative pathway by
which an oxygen atom is transferred from O3 to Fe“ resulting
in the formation of Fe“ (reaction 10). The Fe“ can oxidize
with Fe2+ to Fe3+ (reaction 11) .

Fe2+ + 03 -... (FeO)2+ + 02 ..... (10)

(Fem2+ + Fe“ ...... 2Fe3+ (11)
By this proposed pathway, no additional'OH radicals would be
formed. On the other hand, according to this mechanism Fe“'
does not act as an initiator of ozone decomposition.

Carbonate species (H2CO3*/HCO3'/CO32') , which are commonly

found in natural water, are known to inhibit ozone
decomposition, thus stabilizing ozone. HCO;/COf' do not
directly react with ozone (Hoigné al et., 1985) but react
rapidly with OK radicals to form 'CO,‘ radical, a selective
electrophilic reagent. The 'CO,’ radical also shows a wide range
of reactivities with aromatic compounds however the rate
constants for the reactions of these compounds and 'CO3' radical

are much less than that observed for the reaction of the'same

9
compounds with hydroxyl radicals.

Hydrogen peroxide and UV light are two initiators of
ozone decomposition. Ozone/H55 is a cost effective technique
of advanced oxidation processes. In water, H55 and H0; are in
an acid-base equilibrium of pK.==11.65 (reaction 12). The Hog
ion acts as an initiator of ozone decomposition resulting in
the production of the superoxide ion (reaction 13) . The
superoxide ion may react with an additional ozone molecule to
form the high reactive 'OH radical. At pH <12 when [H202] >10'7M,
HO; has a greater effect on the ozone decomposition rate than
does the OH ion (Staehelin and Hoigné, 1982).

H202 «-~ 1102‘ + 11* ............ (12)

no; + 03 -- on + o,- + 02 ............ (13)
As mentioned above, the higher concentration of hydrogen
peroxide may produce more-OH radicals. But at relatively high
concentrations of hydrogen peroxide, Hg» itself may scavenge
the on radical and inhibit the effect of the on radical on
the oxidation of the target chemical. It was found that with
oxalic and 1,1,2-trichloroethane the rates of oxidation were
fastest with a pH 7.5 and an initial hydrogen peroxide
concentration of 60 to 70 [m (Paillard et al. 1988). The
optimal H55 concentration for removing TCB in OB/Hfih system
was found to be 60 um (Masten et al., 1993).

Ultraviolet light is another common initiator applied to
decompose aqueous ozone in water treatment. In aqueous O3/UV
systems, UV light decomposes ozone and leads to the formation

of hydrogen peroxide (reaction 14) at a rate closely matching

10

the mass transfer rate of ozone into solution (Peyton and
Glaze, 1988).

03 + H20 + UV -- 11,02 + 02 (14)
Hydrogen peroxide then reacts with ozone to produce the highly
reactive OH radical as mentioned above (reaction 12, 13). At
lower pH or higher UV intensities, hydrogen peroxide produces
the hydroxyl radical directly by photolysis (reaction 15)
before it has a chance to react with residual ozone.

H,o,+hv -- 2-0H (15)
The reactions, both hydrogen peroxide undergoes direct
photolysis and.its conjugate base reacts with ozone, result in
the formation of OH radicals that increase system's oxidation
potential.

In short, The impurities existing in real water might
affect the treatment efficiency of ozonation processes by
acting as an initiator, promotor or scavenger. Therefore, in
ozone application, the main chemical characteristics of an
ozonation process should always be reviewed before planning

and performing experiments to optimize an application.

CHAPTER 2

METHODS AND MATERIALS

SYSTEM CONFIGURATION

A continuous flow system was chosen to avoid the
volatilization loss of target compounds and constant the mass
transfer of ozone into solution. The system configuration was
showed in Figure 2.1 and. the experimental apparatus ‘was
summarized on Table 2 . 1. Basically, the continuous flow system
can be partitioned into three parts, production of aqueous

ozone, chemical pumping system, and continuously stirred f low-

through reactor.
1) Production of Aqueous Ozone

A Polymetrics ozone generator (Model T-408, San Jose, CA)
was used to generate ozone gas (approximately 3% v/v ozone in
oxygen) by feeding dried.high.purity oxygen. The dielectric of
the ozone generator was cooled by 10°C water supplied by a
refrigerated circulator (Model 9500, Fisher Scientific) for
the purpose of preventing the dielectric from overheating and
stabilizing the rate at which the ozone gas was generated.
Aqueous ozone solutions were prepared by continuously bubbling
ozone gas into the ozone contactor, a three liter spherical

flask, containing pH 2 water. In order to maintain a constant

11

    
     
 

REFRIGERATEI) CIRCULATOR

 

DCB SOLUTION
BOTTLE

IE

7—

 

DCB SOLUTION
FEEDING PUMP

 

 

NaOH

Hco; PUMP

H303 PUMP

...—...
...-

OZONE GENERATOR

—> MAIN STREAM LINES
SUB-STREAM LINES
GAS LINES

 

 

VENT II

-\

 

 

 

 

O O

()ZONE
CONTAL'TOR

LT;

PH :2

 

 

w‘

AQUEOUS OZONE
FEEDING PUMP

STIRRER MOTOR

WASTE

 

...—......

 

Figure 2.1 The Experimental Configuration of Ozonation system

 

 

S( )LL'TION

 

PH 2 SOLUTION
FEEDING PUMP

 

SAMPLING PUMP

13
water level in the contactor, a peristaltic pump (Model 7520-
25, Cole-Parmer Instruments, Inc.) was used to continuously
pump in pH 2 water and a piston pump ( Model RHSY, Fluid
Metering, Inc.) was used to continuously pump out aqueous
ozone solution; both of the pumps were set at the same
flowrate (~12.5 ml/min). In the ozone contactor, a stir bar
was stirred by a magnetic stirrer to mix the aqueous ozone. A
UV spectrophotometer (Model UV-1201, Shimadzu, Columbia, MD)
was used to monitor aqueous ozone concentration continuously
to ensure the system was stable.
2) Chemical Pumping System
DCB solution, Fe2+ solution, HCO,‘ solution, and H202
solution were respectively pumped by a piston pump (Model
RHSY, Fluid Metering, Inc.) , a syringe pump (Model A..E, Razel

Scientific Instruments, Inc.) , a syringe pump (Model A-99. .ER,

Table 2.1 The List of Experimental Apparatus

 

 

ozone generator T-408 Polymetric

 

Refrigerated Circulator 9500 Fisher Scientific

 

H 2 water Peristaltic Pump 7520-25 Cole-Parmer Instruments

 

 

 

 

 

 

 

Ozone Solution Piston Pump RHSY Fluid Metering

DCB Solution Piston Pump RHSY Fluid Metering

HOO,‘ Solution Syringe Pump A-99..ER Razel Scientific Instruments
Feu'Solution Syringe Pump A..E Razel Scientific Instruments
H55 Solution Syringe Pump A..E Razel Scientific Instruments
NaOH Solution Piston Pump NSI-33R Milton Roy

Photochemical Reactor 7868 Ace Glass

 

 

UV Spectrophotometer UV-lZOl Shimadzu
I E

 

 

 

 

l4

Razel Scientific Instruments, Inc.) , and a syringe pump (Model
A..E, Razel Scientific Instruments, Inc.). These chemicals
were individually discharged to reactor. The flowrate for each
pump was 12.5 mL/min, 1.0 mL/min, 0.6 mL/min, and 0.1 mL/min,
respectively.
3) Continuously Stirred Flow-Through Reactor (CSFTR)

An impeller-stirred photochemical reactor (Model 7868,
Ace Glass, Inc., Vineland, NJ) was used in all experiments.
There are two chambers in the reactor and the total working
volume is 250 mL. A stirred impeller installed in the smaller
chamber provides a adequate mixing in the reactor by
continuously circulating the solution between the two
chambers. The impeller was driven by a stirrer motor,
connected to the impeller by a flexible shaft. All of input
lines were 3positioned below' the impeller blades to 'mix
influent streams rapidly. Trace studies have been done by
Michael J. Galbraith (1993) and it proved that the reactor

could be adequately described by a CFSTR model.

REAGENTS

1) pH 2 water : Deionized water was acidified with 36%
hydrochloric acid to pH 2.

2) DCB solution : A six liter glass flask was filled with 6 L
deionized water. 25 uL of 1,2-dichlorobenzene (99%, Aldrich
Chemical Co., WI) was added in the flask then the flask was
tightly sealed immediately. The solutions were stirred with

magnetic stirrer for three days. The concentration of 1,2-

15
dichlorobenzene solutions resulting from this procedure was
about 4ppm.

3) Fe2+ solution : 20 mL conc H280, was slowly added to 50 mL
deionized water and 0.351 g Fe(NH4)2(SO,)2°6H20 was dissolved
into the acid solution. By diluting it with deionized water
to 1 L, a 50 mg/L Fe2+ solution was prepared and stored in
a dark bottle.

4) H202 solution : 85 pL of 30% H202 (Baker analyzed, Sigma, MO)
was added into 50 mL deionized water to form 0.015 M H202
and it was standardized via direct UV absorption (6240 = 40
M‘1 cm_1) . It was prepared every time before used.

5) Indigo blue solution : 6 grams indigo blue was dissolved in
1 L deionized water and stored in a dark bottle as a stock
solution. Proper amount of stock solution was diluted with
deionized water to an absorbance of ~1.0000 at 600 nm every

time before used.

ANALYTICAL METHODS

The inlet ozone concentration was determined by using
direct UV-absorption method at 258 nm. Inlet aqueous solution
was continuously pumped through a 2 mm quartz flow cell and
was monitored by a UV spectrophotometer (Model UV-1201,
Shimadzu Scientific Instruments, Inc., Columbia, MD). An
extinction coefficient of 3000 M‘1cm'l was used to convert
jabsorbance into mole concentration.
The ozone concentration in the reactor was determined by

using the indigo method (Bader and Hoigné, 1982) . While steady

16
state condition was reached for each experiment, the effluent
solution was directly sampled from the reactor outlet port
with a 150 mL flask containing 100 mL indigo blue solution.
The absorbances of the solution were measured at 600 nm before
and after sampling.

1,2-Dichlorobenzene concentration ‘was measured ‘using
head-space gas chromatograph (Autosystem, Perkin Elmer,
Norwalk, CT) equipped with a flame ionization detector and a
silica glass capillary column (PE624, Perkin Elmer, Norwalk,
CT). The residual ozone was quenched by using sodium nitrite
solution. Internal standard, 0.5 ppm 1,3,5-Trichlorobenzene,
was used in DCB analysis.

The hydrogen peroxide concentration in the reactor was
determined using the peroxidase N,N-diethy-p-phenylenediamine
method with flow injection analysis technique (Galbraith,
1993). Samples were collected at reactor outlet port and were
purged with nitrogen gas during sampling to remove residual
ozone before analysis.

The ferrous ion concentration in reactor was determined
by‘ Phenanthroline ‘method. Samples were also jpurged. with
nitrogen gas during sample collecting for 5 minutes to remove
residual ozone. A standard curve was done for each set of

experiments.

EXPERIMENTAL PROCEDURE
The experiments of this study were listed in Table 2.2.

Each experiment was designed at the same pH including ozone,

17
ozone/UV, and ozone/11,02 system with the same condition. Exp.1~
Exp.6 were designed to investigate the effect of bicarbonate
using 0,, 0,/UV, and O,/H,O2 treatments at vary pH. Additional
Fe“'was added in Exp.7~Exp.10 for investigating the effect of
Feu'when compare with Exp.4~Exp.6.

The experiments were started with pumping DCB solution
and un-ozonated pH 2 water into the reactor. One hour later,
the samples were taken for initial DCB concentration. NaOH
piston pump was turned on to adjust pH in reactor when
necessary. The ozone.generator was turned on and.ozone gas was
bubbled into the contactor. The concentration of aqueous ozone
in the contactor was monitored by UV spectrophotometer
continuously and was controlled at 12 mg/L. HCO; syringe pump
and Fe2+ syringe pump were turned on, if necessary, after

aqueous ozone concentration in the contactor was stable. All

TABLE 2.2 The List of Experiments in This Study

 

 

series pH [HCOg] added [FeHJ added Process

Exp. 1 5.40 0.002 M --- 0,, 0,/Uv, 0,/H,02
Exp. 2 6.10 0.002 M --- 0,, 0,/Uv, 0,/H,02
Exp. 3 7.28 0.002 M --- 0,, 0,/Uv, 0,/H,02
Exp. 4 5.33 0.005 M --- 0,, 0,/Uv, 0,/H,02
Exp. 5 6.01 0.005 M --- 0,, 0,/Uv, 0,,/11,02
Exp. 6 7.35 0.005 M --- 0,, 0,/Uv, 0,/H,02
Exp. 7 2.24 0.005 M 2.0 mg/L 0,, 0,/Uv, 0,/H,02
Exp. 8 4.13 0.005 M 2.0 mg/L 0,, 0,/Uv, o,/H,02
Exp. 9 5.79 0.005 M 2.0 mg/L 0,, 0,/Uv, 0,/H,02
Exp.10 6.29 0.005 M 2.0 mg/L 0,, 0,/Uv, 0,/H,02

 

18
necessary samples (e.g., remaining DCB, ozone, and Fe“) for
the study of ozone system were taken from effluent stream
after reactor had reached steady-state (one hour after all
necessary pumps were turned on). After sampling, the UV light
was turned on and all other equipments were kept at the same
condition. When system reached steady state, effluent stream
were sampled again for ozone/UV study. The UV light was turned
off and H55 syringe pump was turned on. The system was again
allowed to reach steady state before the effluent stream was
sampled for ozone/Hg» study. Whatever the system was changed,

it is necessary to wait for one hour before steady state was

reached. Table 2.3 summaries the experimental condition of all

 

 

 

 

 

 

 

 

 

 

equipments.
Table 2.3 The Operation Condition for Equipments
in Each System
Equipment Initial Ozone Ozone/UV Ozone/H45
Condition system system system
Ozone Generator off on on on
Ozone Pump on on on on
DCB Pump on on on on
HCO, Pump off on on on
UV Light off off on off
H202 Pump off off off on
NaOH Pump off onm onm onm

 

 

 

 

 

 

 

 

Note: (1) The NaOH pump was turned off in Exp. 7.
(2) The Fe“'Pump was turned off in Exp. 1~Exp. 6 and was
turned on in Exp. 7~Exp. 10.

19
The effect of bicarbonate on DCB degradation was studied
with [HCOg] = 2 mM and 5 mM at pH 5, 6, and 7. The desired
bicarbonate concentration in reactor was obtained by pumping
proper concentration of sodium bicarbonate solution into the

reactor with a fixed speed syringe pump.

CHAPTER 3

KINETIC MODEL

THE MODEL MECHANISMS

Based on basic mechanisms of ozone decomposition reported
by Staehelin, Biihler, and Hoigné (has been discussed in
chapter 1), an model to describe ozone decomposition along
with contaminant degradation was developed using 72 reactions
for O3, O,/UV,and 0,,/H202 systems. The reactions used in this
model are listed in Table 3.1.

It is generally accepted that O, decomposition is
initiated by OH‘ (R1) and H0, (R2). The ozone decomposition
rate predicted by these two reactions is much slower than that
observed in acid solution. Thus an additional initiation
reaction, the thermal dissociation reaction of 03 forming O
and 02 (R3) in acidic solution (Sehested et al., 1991), was
incorporated into the kinetics model as well as the initiation
reaction of 03 with OH“ and H023 Contrary to the kf value for R3
that was reported by Sehested et a1. (1991) , 1073". Using this
model, we estimated the kf value to be 6.5*10“s“. The quantum
yield for the production 0 from H202 was also included in this
model. In the presence of UV light, the reactions for the
photolysis of aqueous ozone to produce H202 (R44) and

20

TABLE 3.1 A List of Reactions and Rate Constants

21

Used in the Kinetic Model

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

enemas-rs PRODUCTS nus co Harm“) not
1‘: IE;
1 0, + 0a 110, + 02- 1.4E+02 33
2 0, + HO,‘ 110 + -0,- + 02 2.8E+06 33
3 o, 0 + 02 6.5E-01‘b’ 1.0E+09 31
4 trip, 0 + 14,0 2.6E-04 2.2E+02<") 28
5 0 + H20 'HO + 'H0 8.0E+01<‘” 31
6 0' + H” H0, 2.0E+10 3.2E+05 38
7 02° + 0, -o,- + 02 1.6E+09 6
8 0,; + 11* no, 5.2E+10 3.3E+02 6
9 110, on + 02 1.1E+05 6
10 'OH + 0, M0, 2.0E+09 1.0E+04 34
11 110, so, + 02 2.8E+04 34
12 0' + 02 -0,' 3.0E+09 3.3E+03 14
13 0' + -0,- 20,’ 7.0E+08 5
14 0 + on 1110,- 2.0E+10 30
15 0' + no, 0,‘ + orr 4.0E+08 29
16 0' + 11,02 -0,- + H20 5.0E+08 5
17 0M 0' + 11* 6.3E-02 5.0E+10 38
18 'OH + OH‘ 0' + H20 1.2E+10 1.8E+06 5
19 'OH + -0,- so, + 02- 6.0E+09 3o
20 'OH + no, 0,- + H20 7.5E+09 5
21 on + H20, 110, + [120 2.7E+07 24
22 0' + 0, + H20 ZOH’ + 02 6.0E+08 5
23 02' + 'OH OH + 02 1.0E+10 34
24 02° + 2110, [11,02 + 202 9.7E+07 38
25 02' + so, [011' + 202 1.0E+10 34
_26_0,- + 110, Iorr + 02 + 0, 1.0E+10 _3_4_

 

22

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

TABLE 3.1 (Cont’d)
Renown-rs Deanne-rs nus co NBTANT“) no:
*4 It;

27 0, + 044 OH' + o, 2.5E+09 30
28 “OH + on ,0, 5.0E+09 34
29 014 + 440, ,0 + 0, 6.6E+09 5
30 014 + 440, 14,0, + 0, 5.0E+09 34
31 014 + 410, hip, + 0, 5.0E+09 34
32 440, + 410, [3,0, + 0, 8.7E+05 38
33 440, + 440, ,0, + 20, 5.0E+09 34
34 'HO, + 440, 14,0, + 0, + 0, 5.0E+09 34
35 440, + 440, 14,0, + 20, 5.0E+09 34
36 ,0, + 0, ,0 + 20, 6.5E-03 38
37 1440, + 44* [14,0, 5.0E+10 1.0E-01 38
38 [14,0 [14+ + OH‘ 1.0E-03 1.0E+11 7
39 [14,1304 [14,90; + 14* 3.2E+08 5.0E+10 38
4o hypo,- Iupof + 14* 3.2E+03 5.0E+10 38
41 [14903 I903 + 14* 2.2E-o1 5.0E+11 38
42 [14,00, Inco, + 14* 2.1E+04 4.7E+10 38
43 co, I00,” + 44* 2.2E+00 4.7E+10 38
44 0, + 14,0 + hv I14,0, + 0, 1.5E-02“) 24
45 84,0, + hv 0H + 'OH 1.5E-03<" 38
46 Fe3+ + orr + hv Fe2+ + 014 5.0E+03 10

.4 47 ,po4 + on 44,130, + 41,0 2.7E+06 5
48 Iago,- + 'OH 41,130, + orr 2.0E+04 5
49 hypo; + -0,- lHPOf’ + 440, 9.1E+07 9.1E+06
50 ll-[POX‘ + 014 I'HPO,‘ + orr 5. 9E+05 17
51 [141303 + '0' lUN'KNOWN 3.5E+06 5
52 I90," + “OH I-po,2-+ orr 7 . 0E+06 17

, 53 Eco, + 'OH [4400, + 44,0 1.0E+05 {.3—

 

 

 

 

 

 

23

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

and MJsJ.

(b)
(C)
(d)

 

 

Value estimulated from model simulation.
This reactions are proposed in this work.
Value estimated from structure-reactivity relationships.

 

 

TABLE 3.1 (Cont’d)
No . nuc'rms pnonuc'rs RATE 00 118nm") Ref
1:. x.
54 00,- + 014 00,- + 14,0 1.5E+07 5
55 00,2- + 014 00,- + 014 4.2E+08 5 I)
56 003' + 0' 00,- + 02- 5. 0E+05 14
57 00,- + 0, OWN 1.0E+05 38
58 00,- + -0,- 00,2- 4» o, 7 . 5E+08 14
59 00, + 0, 00,2- + o, 6.0E+07 14
60 00, + 011 OWN 5.0E+09 38
61 00,- + 140,‘ [1100,- + 0,’ 5. 684-07 17
62 00,- + 11,0, [1100, + 140, 8 . 0E+05 17
63 Fe2+ + 03 Fe“ + 0,‘ 1.7E+03“’) 12
64 Fe2+ + 14,0, Fe3+ + 014 + 011 76.5 37
65 Fe“ + 011 Fe“ + 08 4.3E+08 5
66 Fe“ + 0' + 11,0 Fe3+ + 208 3.8E+09 5
67 CB + 0, PRODUCT 2.5E+00 (d)
68 [008 + 110 008 + 11,0 4.0E+09 10 J
69“” IDCB + 00,- 008 + 1100,- 1.0E+05 (d)
70“) 008 + 0, 'OODCB 1.0E+09 (d)
71“) 00008 + 0, 00008 + 014 1.0E+Ol (d)
72“) 00008 + 110 PRODUCT 4.OE+09 (d)
mummmafiu

 

24
decomposition of H,O, to form hydroxyl radicals (R45) are
considered.

Reactions R6~R11 describe the radical chain reaction of
ozone decomposition as published by Staehelin, Bflhler, and
Hoigné (1984) . Superoxide anion ('O,') and hydroxyl radical
(OH) are two radical chain reaction carriers which promote
ozone decomposition. The additional reactions reported by
other authors (R12~R21) were also considered in the model
including the reactions of oxygen anion radical (01 although
'O'is formed only at significant concentrations at high pH. A
hypothetical radical-forming reaction, R5, (Sehested et al.
1991) that would be in direct competition with the reverse
reaction.of R3 was also included in the model. A rate constant
of 8.01|'110‘s'1 was estimated for this reaction (R5) by fitting
the data of Exp.1 to the model (as shown in Table 3.2).

Termination reactions are those reactions which consume
free radicals and shorten the chain length of ozone
decomposition. R22~R36 describe the radical termination
reactions which were included in the model. R37~R43 describe
the proton transfer reactions. These reactions were considered
to be fast equilibrium. processes. Since. they' were also
involved in very fast propagation reactions, they may be in
steady state but not equilibrium.

Carbonate and phosphate species are hydroxyl radical
scavengers which inhibit the radical chain reactions. R47~R62
describe the relative reactions of carbonate and phosphate

species with free radicals. However, the intermediate'CO;

25

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table 3.2 The Estimation of Rate Constants
for Reactions R3 and R5

RateConstant OzoneConc. (M) DCBConc. (M)
km kn: [031.3, [031% [WELL [DCBJmM_

1 . 02:10'7 8 . 0x10" 4 . 99x10‘5 1 . 19x10“ 5 . 05x1043 1 . 26x10’5

1 . 0x10’7 8 . 0x10° 4 . 99x10’5 1 . 1911104 5 . 05x1045 1 . 26x10"

1 . 0x10'7 8 . 0x101 4 . 99x10'5 1 . 19x10“ 5 . 05x10*5 1 . 26x10'5

1 . 0x10” 8 . 0x102 4 . 99x10‘5 1 . 19x104 5 . 05x1045 1 . 26x10'5

6 . 5x10° 8 . 0x10" 4 . 99x10” 3 . 09x10‘5 5 . 05x1045 1 . 05x10"

6 . 5x10° 8 . 0x10° 4 . 99x10’5 2 . 81x10" 5 . 05x10*3 7 . 97x10‘5

6 . 5x10° 8 . 0x101 4 . 99x10’5 1 . 27x10‘5 5 . 05x1045 1 . 87x10“

6 . 5x10° 8 . 0x102 4 . 99x10’5 2 . 91x10‘5 5 . 05x1045 3 . 74x10‘7

6 . 5x10“ 8 . 0x10" 4 . 99x10‘5 8 . 51x105 5 . 05111045 1 . 11x10'5

6 . 5x10" 8 . 0x10° 4 . 99x10'5 7 . 95x10’5 5 . 05x10‘5 1 . 01x10"
65x10‘ 8 0x101 4.99me 534101 50541016174101

6 . 5x10" 8 . 0x102 4 . 99x10" 1 . 50x10" 5 . 05x10“ 1 . 60x10“

6 . 5x10'2 8 . 0x10" 4 . 99x10’5 1 . 14x10" 5 . 05x10“ 1 . 24x10"

6 . 5x102 8 . 0x10° 4 . 99x10'5 1 . 13x10“ 5 . 05x10*5 1 . 22x10°5

6 . 5x102 8 . 0x101 4 . 99x10’5 1 . 00x104 5 . 05x1045 1 . 06x10"

6 . 5x10‘2 8 . 0x102 4 . 99x10’5 5 . 96x10" 5 . 0511104 6 . 051410“s
acts as a promoter in its reaction with H,O,/HO,’ (R61 and R62) .
Fe2+ initiates ozone decomposition by an electron
transfer reaction (R63, R64) . In the meantime, Fe2+ also

scavenges free radicals ('OH and '0') and shortens the chain

reaction (R65,R66) . In the presence of UV light, Fe3+ is
converted to Fe2+ by accepting an electron from OH‘ and forming

the 'OH radical (R46) .

26

Relatively little is known about the mechanism of the
reaction of ozone with DCB. One of the possible reaction.of'OH
radical with organic pollutants suggested by Hoigné (1988) is
H-abstration (R68). The resulting radicals then add to the
oxygen molecule rapidly forming peroxy radicals (R70). The
peroxy radical scavenges another OH forming an unknow’product
(72). R71 is a possible reaction adepted from the model

developed by Yao et al. (1992).

MODEL MODIFICATION FOR CONTINUOUS FLOW SYSTEM

A continuously stirred flow-through reactor was used in
all experiments. Equation 16 shows the differential equation
obtained from.the mass balance of species X in continuous flow
system. The species X could be 0, 0r DCB or '0H etc. . Any one

of them should be expressed by its own differential equation.

 

dIX] _ 1 _ ”
dt '3 ( [X10 [X] ) +§ (19* [reactants] ,) (15)

where [X] is the steady state concentration of species X in
the reactor, tXL,is the initial concentration of species X in
influent stream. 6 is the hydraulic retention time of the
reactor. There are n reactions involving species X. kiis the
rate constant of reaction i. The concentrations of reactants
in the reaction are given by [reactantsjr If the resction is
second order overall (first order in each of the reactant)
then there would be two reactants in the equation, e.g. ,

k,*[reactant,],*[reactant,],. If the reaction is first order

27
then there would only be one reactant term in the equation and
if the reaction is zero order then integer "1" replaces the
[reactant]i term in the equation. The last term of equation 16
summarizes the reaction rates of all reactions involving
species X. If the reaction produces species X, the value of
k,1‘b[reactants]i is a positive. On the contrary, the reaction
consumes species X, the value of k,*[reactants], is a negative.
For each experiment, [X]0 and 9 are constants. Substituting

k'=[X]o/9 and k"=1/9 into equation 16, yields:

 

dLXI= /_ u n _ 17
dt k k [X] +2; (k1*[reactants],) ( I

In equation 17, the first term (k') describes a zero order
reaction forming species X (the reactant is replaced by
integer "1" then the reaction rate is k'*1), and the second
term (k") describes the kinetics of first order reaction
involving species X (the reactant is X and reaction rate is
k"*[X]). Then they can be summarized into the third term by

adding two extra reactions (as shown in equation 18).

1102

 

d[X] -
dt -; (k1*[reactants],) (18)
Where the kn+1= k', [reactants]n+1= "1" and k,+2= 'k":

[reactants]n+,=[X]. Equation 18 is the simplest form of using
differential equation to describe a homogeneous reaction
system, e.g. , the 'HO, generation rate in pure water system

(see page 5) is:

28

dI'H021/dt k1[03] [03'] + k6['Ho4] + an'Hoz] ’ kn['°2'1[H+]
= -E(k§[reactants]g
The reactions that occur in the CFCMR system used in this
study can be modeled with using Acuchem program (Braun et al. ,
1988). The additional reactions for each species are added to
replace the mass flux in/out the reactor.
unknown 1 --—> X , ’=[X]o/6, flux in equation
X --» unknown 2 , k"=1/6 , flux out equation
where 6 = 600 sec. for all experiments, thus, k'= [XLJ600 M

s‘l and k"= 1.671110‘3 54. The model used in Acuchem program is

attached in APPENDIX A.

CHAPTER 4

RESULTS AND DISCUSSIONS

The degradation rates of ozone and DCB in 0,, O,/UV, and
O,/H,O, treatment systems are summarized in Tables 4.1 to 4.3.
Staehelin and Hoigné (1985) and Peyton and Glaze (1988)
reported that bicarbonate and carbonate are hydroxyl radical
scavengers which result in the loss of treatment efficiency of
processes involving '01! radical. The experimental results of
this study agree with those of Staehelin and Hoigné (1985) and
Peyton and Glaze. DCB removal efficiency decreases in 0,,
O,/UV, and O,/H,O, treatments (pH 5~7) when the bicarbonate
concentration of the solution was increased from 0.002 M to
0.005 M (as shown in Table 4.4 and Figures 4.1 to 4.3). It was
also reported that bicarbonate ions do not react with ozone
(Hoigné et al., 1985) but react with hydroxyl radicals and
inhibit ozone decomposition by acting as a hydroxyl radical
scavenger and interrupting the chain reaction. In other words,
ozone is more stable in solutions containing higher
concentration of bicarbonate (Hoigné, 1988) . The hypothesis
mentioned above is contrary to the results of this study as
shown in Figures 4.4 to 4.6. It was found that the degradation

rate of ozone increases in 0,, O,/UV, and O,/H,O, treatments

29

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306336 3.33.2. 30.30006 30430.3 03.30004 3.33.3 0006336 3630.00 0006 05.0
3063006 00630.: 0863006 3.33.2. 3.33.3 00630.00 03.30006 3.300.00 0006 3.0
30.3036 30.3060 30.3306 00330.3 30632.6 3.33.00 03.03006 00.03030 0006 3.0
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00063036 3630.30 03633.0 00.33.00 30.30006 3.33.00 0006 3.0
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000.3036 3.63330 300.0334 3.33.3 30.3036 5.30030 0006 0mg.
3063006 3.33.00 03.3033 2.6.30.3 0006336 3633.03 0006 3.0
306336 3.33.3 30.3306 3.33.2. 306336 00.33.00 306 3.0
.438. .3; :38. .2: :38. .2; $.38. .25
33 06633000 03 3033000 03 39.3033 33 0063633
cowummuumoa H0>060m cowumosummo H0>Oemm caduuosuuoo Hs>080m sawusoeummo H0>080m .20
5300 86:. 56 3000 Zoom. 00
0005003 N03:16:83 3 :00 can :06 :0 .000 no 360 063003000 as, 033.

33

 

65 0.0021111 HC03- - -
50 0.005M HC03- f 5033 i.
35

 

 

DCB Removal Efficiency
l%l

 

 

4 5 6 7 8
pH

Figure 4.1 Effect of Bicarbonate Concentration on DCB Removal Efficiency
in Ozone Treatment System

 

g 0.002M HC03- ‘

90 ,. 0.0051111 HC03- ..Qxx.“‘is . .
t 89.9 “
80 1’-
75 1
7O ’ A - ‘ : A - ‘ : ‘ ‘ 1 ‘ r ‘ ‘ ‘ L—:
4 5 6 7 8

DH ;

 

 

 

lCo-C)/Co
DCB Removal Efficiency
l%l

 

 

 

 

 

Figure 4.2 Effect of Bicarbonate Concentration on DCB Removal Efficiency
in Ozone/UV Treatment System

 

 

CD
01

90.19 '

   

   

 

36.21 - 89.21 = 3-5

'5 ' i .L

oo
01

on

O

>

F

JL
___f_--._0.-l____.__ _“_J

(Co-CilCo
DCB Removal Efficiency
(9%)
{D
o
f
S
’5'

 

4A A A A A A A - A I A A A A

6 7 8
pH

 

4b
01

 

 

Figure 4.3 Effect of Bicarbonate Concentration on DCB Removal Efficiency
in Ozone/H202 Treatment System

34

 

(Co-CHCo
Ozone Consumption i%i

 

 

80 i:

v

60 ‘-

vv '11
l

 

50’

z
.I

., H \u . . ..............................

7O ‘LW...

75.?7 ‘\ T

U' ’ V r

: H 0.002M HC03- ‘

pH

 

Figure 4.4 Effect of Bicarbonate Concentration on Ozone Consumption

in Ozone Treatment System

 

(Co-CHCo
Ozone Consumption (9’0)

 

97 .E
96 {-

 

95

99 T" ogoosM'H‘C'oer“"'“;:

100 if"""

...-98.76 9836

 

 
 

// “ \
" ,/ 98.99 “

 

/1 K‘
- 1 \\

 

 

“...... V .. 3971.05 . WW ‘\_\...\.>Z:97.01
Z 0.002M HC03- "

 

pH

Figure 4.5 Effect of Bicarbonate Concentration on Ozone Consumption

in Ozone/UV Treatment System

W.---__~.AW-- --- ...

 

(Co-C)/Co
Ozone Consumption (%)

 

90

 

70‘
4

100 1W
95 .. .....

A
vifivrvv vv'
!

85 igw
80

75 -- 0.002M HC03-WW.

98.91

 

 

 

 

0.005M HCO3- V’MSBJS

 

 

 

«u -I_

5 6 7
pH

2 95.65 _ 93.57

 

 

Figure 4.6 Effect of Bicarbonate Concentration on Ozone Consumption

in Ozone/H202 Treatment System

35
(pH S~7) when the bicarbonate concentration was increased from
0.002 N to 0.005 M (as shown in Table 4.5). Therefore, the
effect of bicarbonate/carbonate ion cannot be explained simply
by the scavenging of the hydroxyl radical by bicarbonate/
carbonate (Chelkowska, 1992) . However, previous work has shown
'C03‘, which is formed when bicarbonate ions react with “CH
radicals, could scavenge ozone (Nata et al., 1988). An
increase in the bicarbonate ion concentration would result in
a proportional increase in the consumption of hydroxyl
radicals. This would reduce the possibility of the organic

compound reacting with hydroxyl radicals and thus decrease

Table 4.4 The Effect of HCO,‘ on DCB Removal Efficiency

 

 

0.002 14‘ 0.005 14‘ 0.002 14‘ 0.005 14‘ 0.002 14’ 0.005 MI
I 5.4 64.5% 50.8% 94.6% 89.9% 88.2% 89.1% I
I 6.1 58.1% 51.4% 88.6% 87.8% 90.2% 89.2% I

7.3 50.7% 47.0% 85.0% 82.0% 89.1% 88.5% I

* the bicarbonate concentration

 

 

 

 

 

 

 

 

 

 

 

Table 4.5 The Effect of HCO,’ on 03 Degradation Rate

i —

PH 03 03/ UV 03/ I{202
0.002 14‘ 0.005 14‘ 0.002 14' 0.005 11‘ 0.002 14' 0.005 14‘
59.5% 76.0% 97.0% 98.8% 77.3% 96.8%

 

 

 

 

 

 

 

 

 

 

 

 

60.4% 93.6% 96.2%__

5 4
6.1 75.8% 75.9% 99.0% 99.0% 95.6% 98.9%
7 3

*

 

36
removal efficiency of the organic compound. Simultaneously, as
more bicarbonate ions react with hydroxyl radicals producing
more 'CO,‘ this depletes additional ozone. This provides a
reasonable explanation as to why bicarbonate ions would
decrease the treatment efficiency of DCB and increase
degradation rate of ozone.

In addition to these reactions, ‘CO,’ could also react with
excess H202/H02' to form 1102/02“. These products would initiate
the ozone decomposition chain reaction thus accelerating ozone
degradation and increasing the concentration of hydroxyl
radicals. Therefore, the reaction of 8202/30; and 'CO; could
lower the loss of hydroxyl radicals consumed by bicarbonate
ions. This means the excess 8202/302‘ would not only initiate
ozone decomposition but would also reduce the effect that
bicarbonate would have on the removal efficiency of DCB. In
this study, higher I-Izoz/HO; concentrations were present in the
03/11202 treatment system than the other two treatments. As
expected from this explanation, the results show that
bicarbonate ion has less effect on DCB removal in ozone/111202
treatment than it in ozone and ozone/UV treatments (as shown
in Table 4.4).

Fe2+ initiates ozone decomposition and results in the
formation of the ozonide ion, which can then decompose to from
the hydroxyl radical (Hoigné et al. , 1985) . As such, F'e2+ acts
as an initiator. On the other hand, excess Fe2+ also consumes
hydroxyl radicals and terminates the radical chain reaction.

As such, Fe2+ can also act as a scavenger. For the ozone

37

treatment process, the concentration of ozone in the reactor
was ~30 um before Fe2+ was added. Under these conditions, Fe2+
could react with ozone and accelerate ozone decomposition to
form more hydroxyl radicals. Thus, both DCB removal efficiency
and ozone consumption are increased. In our system, we
observed an increases about 16.9% and 12.6% in the DCB removal
and O3 consumption, respectively, by the addition of Fe2+ at pH
6 (as shown in Table 4.6 and Figure 4.7 8 4.10). In ozone/UV
and ozone/11202 treatments, the concentration of ozone remaining
(less than 2 1414 in ozone/UV and less than 4 pH in ozone/H202)
before Fe“ were added was very small. Fe2+ has to compete with
other initiators for the small amount ozone present. Only a
small portion of the Fe2+ added would compete with other
initiators to react with ozone and the excess Fe2+ would
scavenge the hydroxyl radical and thus inhibit the extent to
which the the hydroxyl radical oxidizes DCB. Hence, the

Table 4.6 The Effect of Fe2+ on DCB and 03
Degradation Rate at pH 6

         
 

 

 

 

 

 

Oa/UV 03/3102
EDGE} [0:] EDGE} [031 [DCB] [03]
I Exp.5m 51.4% 76.0% 87.8% 99.0% 89.2% 98.9%
Exp.9“’ 67.7% 90.4% 84.7% 99.2% 87.0% 97.7%
lExp.10‘” 68.9% 86.7% 80.7% 99.0% 85.7% 98.0%
Diff.“ 16.9% 12.6% -5.1% 0.1% -2.9% -1.1%

 

 

 

 

 

 

Note: (1) The experimental conditions are shown in Table 2.2

(2) Diff. = [(Exp.9 + Exp.10) / 2] - Exp.5

 

38

 

 

80 1
70 1:.-.”
60 1:......
50 ‘
4O 1%.“.--

(9%)

30 {-

(Co-C)/Co
DCB Removal Efficiency

10%

 

 

 

 

 

..... ‘wm-w-(_ Wm- .wss
vWde.WMM m-“39 ........................ a ...................
..... w wxo Fem» , _ l
20 4E-.~.T .. ,1
A 14.12

 

 

100
90
80

(96)

70

(Co-Cl/Co
DCB Removal Efficiency

60

 

50-

 

\Mme W,.;;@

 

 

 

 

 

 

Figure 4.8 Effect of Fe(II) on DCB Removal Efficiency in Ozone/UV Treatment System

 

 

 

100 1
90%
80 13-....-
70%

 

89.21

 

   

wMFflmmemmw

 

 

 

 

 

 

(96)

60%

(Co-C)!Co

 

 

 

 

DCB Removal Efficiency

 

 

 

50 _............ , w/ Fe(II) ; ........
4O ‘Emm /,- : .. -... ......

: ‘ 34.05 i - 1
30 ‘E g- ................. . ; ...
20 ' r r * 1 ~ 1 1 4 A ¢ - - - e - Afi-

 

 

Figure 4.9 Effect of Fe(II) on DCB Removal Efficiency in Ozone/H202 Treatment System

 

41

39

 

 

(Co-Cl/Co’ ‘
Ozone Consumption (%l

90 ' ... . ,_ 90.29

 

80 ‘1

 

 

A A A A A A A A A A A A A A4 A AA! A A A A A A A
v I v V 7

 

 

(Co-Cl/C
Ozone Consumption (%l

 

98.51:- ----- r"
97 --

 

 

 

-.--.-_._..-.-..-. _.__.._...... .--

 

Figure 4.11 Effect of Fe(II) 0n Ozone Consumption in Ozone/UV Treatment System

 

 

lC0-CllC0
Ozone Consumption (%l

 

98.91- .................... . ...... - w/o Fe(II)

W,"

"98.98 I
97 - '

 

94 1%

 

.
h . . ; -
’ _,,
. {/II .
n . . : .
I

 

88 3-...X.. 88.46 . ...;.. .. .. ...... .g -

 

p - - ~ - .
A 4A A A A A A 4 4 A A A A _A I A L A A A A A A A A A A A A
V V I I 1'

 

 

 

Figure 4.12 Effect of Fe(II) on Ozone Consumption in Ozone/H202 Treatment System

 

4O

residual ozone concentration in O3/UV and 03/1120, treatment
systems would not be expected to change significantly. At pH
6, the observations of less than 1% difference in the ozone
consumption and the less than 6% and 3% decrease in DCB
removal efficiency in 03/UV and 03/11202 treatment systems
respectively (as shown in Table 4.6 and figure 4.8, 4.9, 4.11,
4.12) are consistent with the hypothesis mentioned above. As
such, the role of F'e2+ as initiator or scavenger will depend
on the competitive ability of Fe2+ with other initiators for
ozone.

The rate constant of the lieu/03 reaction was modified by
using kinetic model simulation to get a better data fitting.
When the value 5*105 H‘s" (Hoigné,1985) was used in model, the
model predicted that greater than 80% of ozone would have
reacted with Fe2+ immediately and the extent of DCB removal
was overpredicted. However, a smaller rate constant for 1='e”'/O3
reaction (137*th3 H‘s“) was estimated using the model and used
in this study (as shown in Table 4.7).

The results obtained from using the kinetic model to
simulate the observations made in all experiments in this
study are summarized in Appendix B. Comparing the model
simulations for ozone consumption and DCB removal efficiency
with those obtained experimentally, one observes that the best
results for the model simulation are obtained for ozone/UV
treatment followed by for ozone treatment and lastly for
ozone/th treatment. The percentage difference between model

simulations and experimental results for ozone consumption and

41

Table 4.7 The Estimation of the Rate Constant
for Fe”/O3 Reaction

Rate ConStant

     
   

 

i31.7x10‘

    

5.0x10’i

   
 

 

     

03 [0,] 2 . 69x10~’ 198x104 1. 83x10" 1. 82x10"

system [DCB] 4.34x10“l§.44x10‘l 3.98x10“ 311x10‘292xlO‘IZ91x10“

 

 

 

we“) 7.48x10‘Iz-00x10"| 83310“ 51.575381?1.76:10’7l6-08x10"

 

0,,/UV [03] 1.26x10‘ls.46x10‘ 5.72x10‘ 406x10‘327x10‘ 3.12x10‘
system [DCB] 2.69x10‘lm59xlo‘I 2.45x10* 192x10‘1.46x10* 1.37:10‘

 

 

 

[pefl] 5,42x10411.73x10-5I 1.43:104 60:31:10“ l.lelO“|3.76xlO"

 

[o3] 2.43x10“ll.98x10"[1.39xlO" 597x10‘2.17x10" 1.86x10"

 

 

03/11202 [DCB] 2.00XlO"lZ.84xlO‘] 2.38x10“ 169210‘1.24x10‘|1.13x10‘
system we“) 7.80x1041.22x10-’]8.33::10‘ 393x10‘144x10q596x10"

 

 

[14,02] Leona-12.40am] 2.64x10" 145x1470xlO“ 2.992.104

 

 

 

 

 

 

 

 

* The unit for rate constant and concentration are It's"
and M, respectively.

DCB removal efficiency, respectively, at neutral pH are < 15%
and < 16% for ozone treatment, < 4% and < 6% for ozone/UV
treatment, and < 21% and < 14% for ozone/H202 treatment (see
Table 4.8).

As stated previously, 'CO,‘ might consume the excess ozone
and react with other species. In the ozone/UV process, ozone
is decomposed by UV light at a much faster rate than that
observed for O3 in the other two treatment processes. As such,
CD,“ would be expected to deplete very little ozone in ozone/UV
treatment system while the reaction of 'CO,‘ and ozone might
have only a very slight affect on the efficiency of DCB

removal by the ozone/UV process. In contrast, the 'CO3°/O3

42

Table 4.8 The % Difference Between Model Simulations
and Experimental Results at Neutral pH

 

Ozone Degradation Removal

DCB Removal Efficiencyl

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

   
   

  

          

Model Experi. Diff._'_ Model Experi. Diff.‘ I
Exp.2 61.1% 75.8% -14.7% FIG-0;! 58.1% 2.4%
03 I Exp.3 68.8% 60.4% 8.4% 65.5% 50.7% 14.8%
Systeml Exp.5 61.0% 76.0% '15.0% 59.7% 51.4% 8.3%
Exp.6 66.1% 71.4% '5.3% 59.3% 47.0% 12.3%
Exp.9 86.9% 90.3% -3.4% 83.8% 67.8% 16.0%
_ Exp.10 83.2% 86.7% -3.5% 77.6% 68.9% 8.7%
Exp.2 95.2% 99.0% '3.8% 89.8% 88.6% 1.2%
O3/UV Exp.3 95.3% 97.0% -1.7% 85.0% 85.0% 0.0%
System: Exp.5 95.2% 99.0% -3.8% 86.5% 87.8% -1.3%
Exp.6 95.1% 98.4% “-3.3% 77.3% 82.0% -4.7%

Exp.9 96.7% 99.2% -2.5% 89.8% 84.7% 5.1% I
1__ 99 . 0% *2.4_ 6.2% 80. 7%. 5%

 

 

 

 

 

 

 

 

* Diff. is equal to Model(%)

 

 

 

 

 

 

 

95.7% -18.4% 77.3% 90.2% -12.9%
O3/H202I Exp.3 92.5% 93.6% -1.1% 87.3% 89.1% -1.8%
System] Exp.5 78.1% 98.9% -20.8% 76.3% 89.2% -13.0%
Exp.6 90.9% 96.2% -5.3% 80.6% 88.5% -7.9%
Exp.9 94.9% 97.7% -2.8% 91.2% 87.0% 4.2%
Iii-3:13.10 95.0% J8.0% -3.0% 87.8% 85.7% 2.1% ‘

- Experi.(%).

 

 

reaction would be expected to affect the efficiency of the

ozone, and ozone/H4» treatment systems more than observed in

the ozone/UV process.

However, in the model, the rate constant used for the reaction

of 'CO,‘ and O3 is small (10’ dm3 mol" s") (Holcman et al. , 1982) .

43

As a result of the use of this rate constant, the model
predicts that 'CO; would not influence the ozone consumption
in either ozone/UV, ozone, ozone/H55 systems. However, only
for the ozone/UV system is this prediction verified
experimentally. As such, the model simulation and experimental
results are comparable only for the ozone/UV system. However,
the rate of the -CO,'/O, reaction needs to be verified in a
future study.

For the model simulation, the reactor was assumed to be
a complete mixed system. However, the reactor would be more
like a system between complete mixing and plug flow because
all of the influent streams were installed in one location.
The differences between complete mixed and plug flow systems

would result some simulation error by using this model.

CHAPTER 5

CONCLUSIONS

CONCLUSIONS

The effect of bicarbonate on ozonation processes cannot
be simply explained only by the scavenging of the 'OH radical
by bicarbonate. The competition of the intermediate “CO3' with
other chemicals for ozone is an other important mechanism
which should be considered when studying the influence of
bicarbonate on ozonation processes. Thus, in 03, O3/UV, and
03/H202 systems, the removal efficiency of DCB decreases and
the consumption of ozone increases in the presence of
bicarbonate. Furthermore, the reaction in which 'CO,‘ reacts
with HZOZ/HOZ' to form 'HOzl'Oz’, thus initiating the ozone
decomposition chain reaction to form 'OH radicals would
minimize the effect of bicarbonate on DCB removal efficiency.
The 0,,/11202 system has a higher H202 concentration than 03 and
O3/UV systems do. Thus the bicarbonate has less effect on DCB
removal efficiency in O3/H202 system than it does in 03 and
O3/UV systems.

The ferrous ion acts as of both an initiator and a 'OH

radical scavenger in ozonation processes. In the 0, system,

44

45
Fe“ acts as an initiator of ozone decomposition, resulting in
the formation of additional OH radicals, thus increasing DCB
removal. On the contrary, in O3/UV and O3/H202 systems, Fe“ is
unable to compete with UV and H45 as an initiator of ozone
decomposition. Instead, Fe“ acts as an OH radical scavenger,
hence the DCB removal efficiency decreases. As such, the role
of Fe“ as an initiator or scavenger will depend on the
competitive ability of Fe“'with other initiators for ozone.

A rate constant of Fe“/O3 reaction, 1.7x103 M‘s“, was
estimated by model fitting in this study. It is two order of
magnitude lower than that reported by Hoigné et a1. (1985). It
may be caused by the difference of the water quality. Because
the impurities existing in the water may react with Fe“y thus
Fe“ was consumed more than it should be on Fe“/O, reaction
rate estimation. However, this rate constant needs to be
confirmed in the future study.

Good agreement between data from experimental results and
the kinetic model is observed for DCB and ozone degradation
data in the pH range S~8. This is especially true for the
03/UV system, where there are < 4% and < 6% differences
between experiments and kinetics model for DCB and ozone
degradation, respectively.

In water treatment, using ozonation processes is a good
choice to remove lower concentrations of organic chemicals
from water. For process engineers who want to apply ozone most
effectively, the kinetic model can give a general idea of the

target compound’s treatment efficiency. However, due to lack

46

of knowledge of the specifics of ozone chemistry, the kinetic

model does not accurately predict the ozone decomposition rate

or the extent of DCB removal for all conditions. As such,

without such a model, it is always necessary to perform bench

scale studies prior to design and implementation of the plan.

FUTURE RESEARCH

(1)

(2)

In the study of O3/H202 system, we found in the presence of
Fe“, the remained H20, concentration increases when pH was
increased. Lack of the knowledgement of the Fe“/H202
interaction, thus more mechanistic research is necessary
to identify the effect of Fe“ in Gall-1202 system.

The rate constant of Fe“/O3 reaction obtained by model
fitting in this study is lower than the one reported by
Hoigné et al. (1985) . Thus it is necessary to identify the

rate constant of Fe“ /O, reaction in future research.

( 3) The model was only applied in neutral pH in this study. At

(4)

pH >10, the OH is predicted to be the dominate initiator.
However, it is necessary to compare the experimental
results and the kinetic model simulations at high pH when
the OH‘ ion becomes the dominate initiator.

The reactions R67~R72 (see Table 3.1) are the proposed
mechanisms of DCB oxidation. Thus the results of the model
prediction might be changed if different mechanisms of DCB
oxidation were proposed in the model. Thus identifying the

mechanisms of DCB oxidation is necessary in future

research.

1)

2)

3)

4)

5)

6)

7)

8)

9)

10)

LIST OF REFERENCES

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Abukhudair, M.Y., S. Farooq, and M.S. Hussain. 1989.
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Bailey, P080 0 1982. . . . . .
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11)

12)

13)

14)

15)

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20)

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Hoigné, J. and H. Bader. 1983. Rate.Constants of Reactions
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Holcman, J., K. Sehested, E. Bjergbakke, and E. J. Hart.
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Klaning, U.K., K. Sehested, and T. Wolff. 1984. Ozone
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Lamb, J.J., L.T. Mollna, C.A. Smith, and M.Ju Mollna. 1983
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Masten, S.J. and J. Hoigné. 1992. Comparison of Ozone and
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Hydrocarbons in Water- Qz9ne.§cisnss_§_finsinssrins-
14:197-214.

Masten, S.J. and S.H.R. Davies. 1992. Use of Ozone and
Other Strong Oxidants for Hazardous Waste Management.

Ad_ansss_in_En2ir2nmsntal_Scisnsss_and_lsshnslesxl
Qxidants_in_ths_znxirgnmsnt. John Wiley 8 Sons Pub1-. New
York

Masten, S.J., M.J. Galbraith, and S.H.R. Davies. 1993.
Oxidation of Trichlorobenzene using Advanced Oxidation
Processes. Proceedings of the 11th Ozone World Congress

22)

23)

24)

25)

26)

27)

28)

29)

30)

31)

32)

33)

49

Neta, P., R.E. Huie, and A.B. Ross. 1988. Rate Constants
for Reactions of Inorganic Radicals in Aqueous Solution.
J. Phys. Chem. Ref. Data, 17:1027-1284.

Nowell, L.H. and J. Hoigné. 1987. Interaction of Iron(II)
and.Other Transition Metals with.Aqueous Ozone. 8th Ozone
Would Congress, September 15-18.

Peyton, G.R. and W.H. Glaze. 1988. Destruction of
Pollutants in Water with Ozone in Combination with
Ultraviolet Radiation. 3. Photolysis of Aqueous Ozone.
Environ. Sci. Technol. 22(7):761-767.

Razumovskii, S.D. and G.E. Zaikov. 1984. ngng_gn§_1;§

Bsasti2n5.xith_9rsanis_gcsssundso Elsevier Science
Publishing Company, Inc., New York, NY. Chapter 5.

Rice R.G. and M.E. Browning. 1981. ngng_11gatmgnt_gfi

W. Noyes Data Corporation, New Jersey.
Section 6.

Roth, J.A., W.L. Moench, Jr., and K.A. Debalak. 1982.
Kinetic Modeling of the Ozonation of Phenol in Water.
Journal WPCF, 54(2):135-139.

Sauer, M.C., Jr., w.c. Brown, and E.J. Hart. 1984. 0(fin
Atom Formation by the Photolysis of Hydrogen Peroxide in
Alkaline Aqueous Solutions. J. Phys. Chem. 88(7):1398-
1400.

Sehested, K., J. Holcman, E. Bjergbakke, and E.J. Hart.
1982. Ultraviolet Spectrum and Decay of the Ozonide Ion
Radical, 0;, in Strong Alkaline Solution. J. Phys. Chem.
86(11):2066-2069.

Sehested, K., J. Holcman, E. Bjergbakke, and E.J. Hart.
1984. Formation of Ozone in the Reaction of OH with O;
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J. Phys. Chem. 88(2):269-273.

Sehested, K., H. Corfitzen, J. Holcman, C.H. Fischer, and
E.J. Hart. 1991. The Primary Reaction in The Decomposition
of Ozone in Acidic Aqueous Solutions. Environ. Sic.
Technol., 25(9):1589-1596.

Sotelo, J.L., E.J. Beltran, and M. Gonzalez. 1989. Effect
of High Salt Concentrations on Ozone Decomposition in
Water. J. Environ. Sci. Health, A24(7):823-842.

Staehelin, J. and J. Hoigné. 1982. Decomposition of Ozone
in Water: Rate of Initiation by Hydroxide Ions and '
Hydrogen Peroxide”. Environ. Sci. Technol. 16(10) :676-681.

34)

35)

36)

37)

38)

50

Staehelin, J., R.E. Bfihler, and J. Hoigné. 1984. Ozone
Decomposition in Water Studied by Pulse Radiolysis. 2.
OH/HO, as Chain Intermediates". J. Phys. Chem. 88(24):
5999-6004.

Staehelin, J. and J. Hoigné. 1985. Decomposition of Ozone
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Ozone World Congress. WW

Treatment, 2:3-20-72-vs-20-86.

Waite, T.D. and F.M.M. Morel. 1984. Photoreductive
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Yao, C.C.D., W.R. Haag, and T. Mill. 1992. Kinetic
Features of Advanced Oxidation Processes for Treating
Aqueous Chemical Mixtures. Chemical Oxidation Technology
for the Nineties, Second International Symposium. February
19-21, 1992.

APPENDIX A

The Kinetic Model of Ozonation Processes
for ACUCHEM Computer Program

51

;This is a kinetic model of ozonation processes for ACUCHEM
;Ozone/Fe(II)/UV System at pH 6.3

1111
; ----- The Mechanisms -----
; ----- Initiation Reactions -----
03 + OH- = .OHZ + .02- , 1.4E2
03 + HOZ- = .HO + .02- , 2.8E6
03 = 0 + 02 , 6.5E-1
0 + 02 = 03 , 1.0E9
H202 = 0 H20 , 2.6E-4
0 = H202 , 2.2E2
--- Propagation Reactions -----
, 0 = .HO .HO 8.0E1
, .02- + H = .H02 2.0E10
, .H02 = .02- H 3.2E5
, .02- + 03 = .03- 02 1.6E9
, .03- + H = .H03 5.2E10
, .H03 = .03- H 3.3E2
, .H03 = .OH 02 1.1E5
, .OH + 03 = .H04 2.0E9
, .H04 = .OH 03 1.0E4
, .H04 = .H02 02 2.8E4
, .0- + 02 = .03- 3.0E9
, .03- = .0- 02 3.3E3
, .0- + .03- = .02- .02- 7.0E8
, .0- + .OH = H02- 2.0E10
, .0- + HOZ- = .02- + OH- 4.0E8
, .0- + H202 = .02- + H20 5.0E8
, .OH = .0- + H 6.3E-2
, .0- + H = .OH 5.0E10
, .OH + OH- = .0- + H20 1.2E10
, .0- = .OH + OH- 1.8E6
, .OH + .03- = .H02 + .02- 6.0E9
, .OH + HOZ- = .02- + H20 7.5E9
, .OH + H202 = .H02 + H20 2.7E7
----- Termination Reactions -----
, .o- + .02- = OH- + 02 , 6.0E8
, .02- + .OH = OH- + 02 , 1.0E10
, .02- + .H02 = H202 + 04 , 9.7E7
, .02- + .H03 = OH- + 04 , 1.0E10
, .02- + .H04 = OH- + 05 , 1.0E10
, .03- + .OH = OH- + 03 , 2.5E9
, .OH + .OH = H202 , 5.0E9
, .OH + .H02 = H20 + 02 , 6.6E9
, .OH + .H03 = H202 + 02 , 5.0E9
, .OH + .H04 = H202 + 03 , 5.0E9
, .H02 + .H02 = H202 + 02 , 8.7E5
, .H03 + .H03 = H202 + 04 , 5.0E9
, .H03 + .H04 = H202 + 05 , 5.0E9
, .H04 + .H04 = H202 + 06 , 5.0E9
, H202 + 03 = H20 + 04 , 6.5E-3
, 04 = 02 + 02 , 1.0E20
, 05 = 03 + 02 , 1.0E20

I

I

I

“~““““‘~‘

“““‘~\‘

I
I
I
I

“““~

52

I

‘\§““““\“

““

“““

I

1.0E20

1.0E-3
1.0E11
1.0E-1
5.0E10
3.2E8
5.0E10
3.2E3
5.0E10
2.2E-1
5.0E11
2.1E4
4.7E10
2.2
4.7E10

1.5E-2

1.5E-3
5.0E3

4.0E9

06 = 03 + 03
Proton Transfer Equilibrium -----
= OH- + H
OH- + H =
H202 = H02- + H
H02- + H = H202
H3PO4 = H2P04- + H
H2P04- + H = H3P04
H2PO4- = HPO4-2 + H
HP04-2 + H = H2P04-
HP04-2 = P04-3 + H
PO4-3 + H = HPO4-2
H2C03 = HCO3- + H
HCO3- + H = H2CO3
HCO3- = C03-2 + H
CO3-2 + H = HCO3-
----- Effect of UV Light -----
03 = H202 + 02
H202 = .OH + .OH
Fe(III)+ on- = Fe(II) + .OH
- Effect of Phosphate Species
H3P04 + .OH = .H2P04 + H20
H2PO4- + .OH = .H2PO4 + 0H-
H2P04- + .03- = HP04-2 + .H03
HP04-2 + .H03 = H2PO4- + .03-
HPO4-2 + .OH = .HP04- + 0H-
HP04-2 + .0- = UNKNOWNl
P04-3 + .OH = .PO4-2 + 0H-
- Effect of Carbonate Species
H2CO3 + .OH = .HCO3 + H20
HC03- + .OH = .C03- + H20
CO3-2 + .OH = .CO3- + 0H-
CO3-2 + .O- = .C03- + 0-2
.C03- + 03 = UNKNOWNZ
.CO3- + .02- = CO3-2 + 02
.C03- + .03- = CO3-2 + 03
.C03- + .OH = UNKNOWN3
.C03- + H02- = HC03- + .02-
.C03- + H202 = HC03- + .H02
Effect of Iron -----
Fe(II) + 03 = Fe(III)+ .O3-
Fe(II) + H202 = Fe(III)+ .OH
Fe(II) + .OH = Fe(III)+ OH-
Fe(II) + .O- = Fe(III)+ OH-
----- DCB Degradation -----
DCB + 03 = DCB
DCB + 03 = PRODUCTl
DCB + .OH = .DCB
DCB + .C03- = .DCB
.DCB + 02 = .OODCB
.OODCB + 03 = .OODCB + .OH
.OODCB + .OH = PRODUCTZ
----- Modification

for Continuous Flow -----

I

“““‘““‘““““““““‘~“‘“\““‘§““~“

8
08-

03

02

0

.0-

.02-
.03-

.08

.H02
.803
.804
H202
H02-
H3PO4
H2P04-
HPO4-2
904-3
.HPO4-
.PO4-2
82003
8003-
003-2
.HC03
.003-
Fe(II)
Fe(III)
DCB

.DCB
.OODCB
UNKNOWNl
UNKNOWNZ
UNKNOWN3
PRODUCTl
PRODUCTZ

H
OH-
03
02
DCB
H202

Fe(II)

H2CO3
HCO3-
CO3-2
H3PO4

H2P04-
HPO4-2

PO4-3

I
I
I
I
I
I
I
I
I
I
I
I
I

I

“““~““~‘\““\‘V“““‘\“““

53

1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3
1.67E-3

. ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘Q ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘0

Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux

Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out
Out

9.58E-6

2.90E-15

2.08E-7
3.33E-7
1.95E-8
0.00

5.70E-8
8.00E-6

‘. ‘0 ‘0 ‘0 ‘0 ‘0 ‘0 ‘.

6.88E-10;
7.43E-18;

0.00
0.00
0.00
0.00

‘0 ‘0 ‘0 ‘0

I

Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux
Flux

END of Reaction Mechanism Statement:
Initial Concentrations of Species
, 5.75E-3

I

H

In
In
In
In
In
In
In
In
In
In
In

1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600
1/600

Hydraulic Detention Time is 600 Seconds -----

s-1

l
Hlflthi‘P‘thh‘Hi-F‘HidF‘Hi-P‘H

1.:

s-1
s-l

[H]/600
[OH-]/600
[031/600
[021/600
[DCB]/600

[82021/600
[Fe(II)]/600
[820031/600
[8003-1/600
[003-21/600
[H3PO4J/600

In [H2PO4-]/600
In [HPO4-2]/600

In

(M)

[PO4-3]/600

M*s-l
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1
M*s-1

54

OH- , 1.74E-12
o3 , 1.25E-4
02 , 2.00E-4
DCB , 1.17E-5
Fe(II) , 3.42E-5
8202 , 0.00
H2CO3 , 4.80E-3
8003- , 4.13E-7
C03-2 , 4.46E-15
H3P04 , 0.00
H2PO4- , 0.00
904-3 , 0.00
END of Species Concentration Sequence:
;--- Integration Tolerance ---
1.0E-8
;--- Reaction Time (sec) ---

6.0E2

APPENDIX B

The Results of Kinetic Model Simulation

55

Table B.1 The Input/Output Data of Kinetic Model
for Ozone Treatment System

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp. No.‘” Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5
pH 5.40 6.10 7.28 5.33 6.01
[8*] 3.98E—6 7.94E—7 5.25E-8 4.68E-6 9.77E-7
[OH‘] 2.51E—9 1.26E—8 1.91E-7 2.14E-9 1.02E-8
INPUT [031 1.23E-4 1.20E-4 1.23E-4 1.25E-4 1.22E-4
DATA [0210) 2.00E-4 2.00E-4 2.00E-4 2.00E-4 2.00E-4
[DCB] 1.42E-5 1.21E-5 1.21E-5 1.33E-5 9.69E-6
[Fe“] -------------------------
[H2C03] 1.88E-3 1.32E-3 2.12E-4 4.53E-3 3.35E-3
[HCO3’] 2.21E—4 7.78E-4 1.89E—3 4.65E-4 1.65E-3
__ [0032-1 3__3E-9 5.34E-8 1ws.4.88
[031 5.34E-5 4.67E—5 3.84E-5 5.37E-5 4.76E-5
[DCB] 6.17E-6 4.78E-6 4.18E-6 5.73E-6 3.9OE-6
[Fe“] -------------------------
MODEL [8,0,1 1.19E-5 8.66E-6 2.17E-6 1.15E-5 7.70E-6
OUTPUT [802-1 6.21E-12 2.28E-11 8.27E-11 5.26E-12 1.69E—11
08 5.64E-13 6.52E-13 6.88E-13 5.67E—13 6.03E-13
802 2.73E-13 1.88E-13 1.46E-13 3.02E-13 1.98E-13
~80, 4.20E-13 4.52E-13 2.77E—13 4.35E-13 4.60E-13
80, 1.59E-12 1.60E-12 1.39E-12 160E-121.51E-12
EXP. [031001; 4.99E-5 2.9OE-5 4.89E-5 3.00E-5 2.94E-5
RESULT [DCBJOut 5.05E-6 5.09E-6 5.96E-6 6.54E-6 4.71E-6
[Fe“]Out -------------------------
__ __

 

 

 

 

 

 

 

 

 

56

 

 

 

 

 

 

 

 

 

 

 

       

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B.1 (Cont'd)
Exp. NO m Exp. 6 Exp. 7 Exp. 8 Exp. 9 Exp.10
pH 7.35 2.24 4.13 5.79 6.29
[H+] 4.47E-8 5.75E-3 7.41E-5 1.62E-6 5.14E-7
[OH'] 2.24E-7 1.74E-12 1.35E-10 6.17E-9 1.95E-8
INPUT [0,] 1.31E-4 1.26E-4 1.15E-4 1.21E-4 1.18E-4
DATA [02]“) 2.00E-4 2.00E-4 2.00E-4 2.00E-4 2.00E-4
[DCB] 1.29E-5 1.17E-5 1.17E-5 1.35E-5 1.39E-5
[13'8“] ----- 3.42E-5 3.42E-5 3.51E-5 3.32E-5
H2003 4.25E-5 4.8OE-3 4.77E-3 3.67E-3 2.48E-3
H003 4.57E-3 4.13E-7 3.08E-5 1.13E-3 2.32E-3
C032’ 6.01E-6 4.46E-15 2.44E_ 4.28E-8 2.65E-7
[011 4.44E-5 8.31E-6 8.25E-6 1.59E-5 1.98E-5
[DCB] 5.25E-6 7.54E-7 8.54E-7 2.19E-6 3.11E-6
[862+] ----- 3.08E-6 3.16E-6 1.98E-6 1.54E-6
MODEL [H202] 1.90E-6 1.18E-6 1.13E-6 5.70E-7 7.31E-7
IOUTPUT [H02'] 8.63E-11 4.13E-16 4.26E-14 8.07E-13 3. 123-12
'01! 4.65E-13 6.04E-12 5.28E-12 1.82E-12 1.1lE-12
'H02 1.26E-13 1.99E-9 1.64E-113.21E-131.64E-l3
'HO, 2.34E-13 1.07E-12 9.91E-13 9.03E-13 7.70E-13I
1.09E-12 2.64E-12 2.29E-12 1.52E-12 1.16E-12
EXP. [031001; 3.74E-5 4.86E-5 1.12E-5 1.17E-5 1.56E—5
[D08100t 6.83E-6 1.0oE-5 3.22E-6 4.35E—6 4.34E-6
[86“1001: ----- 3.93E-6 8.18E-6 9.36E-6 7.48E-6
Note: (1) The experimental numbers are listed in Table 2.2

(2) The oxygen concentration is an estimated value in
this work.

 

 

57

Table B.2 The Input/Output Data of Kinetic Model

for Ozone/UV Treatment System

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Exp. 86.“) Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5
p8 5.40 6.1 7.28 5.33 6.01 I
[8*] 3.98E-6 7.948—7 5.258—8 4.68E-6 9.77E-7l
[OH'] 2.51E-9 1.26E-8 1.918-7 2.148-9 1.02E-8l
INPUT [O3] 1.268-4 1.208-4 1.23E-4 1.26E-4 1.248-4
DATA [0210’ 2.00E-4 2.00E-4 2.00E-4 2.008-4 2.00E-4
[DCB] 1.42E-S 1.21E-5 1.218-5 1.338-5 9.698-6
[Fe“] -------------------------
8,003 1.88E-3 1.32E-3 2.128—4 4.53E-3 3.35E-3
8001- 2.218-4 7.788-4 1.898-3 4.658-4 1.65E-3
0032- 3.03E-9 5.34E-816.9E-6 5.848-9 9.8988
[03] 6.14E-6 5.88E-6 5.788-6 6.308-6 6.05E-6
[DCB] 1.108-6 1.298-6 1.82E-6 1.248—6 1.338-6
[Fe“] -------------------------
MODEL [11202] 1.318-5 1.20E-5 7.998-6 1.198-5 9.768-6
OUTPUT [802'] 6.86E-12 3.17E-11 3.17E-10 5.468—12 2.15E-1 .
-08 4.90E-12 3.59E-12 2.138—12 3.938-12 2.518-12
~80, 1.7lE-12 5.83E-13 2.578-13 1.988-12 7.188-13
803 5.62E-13 6.20E-13 4.088-13 5.908-13 6.97E-l3
h _ -8_, * 1.588—12 1.118-12 6.48E-13.30E-12
[O,1Out 3.17E-6 1.218-6 3.698-6 1.568-6 1.288-6
RESULT [D081Out 7.608-7 1.38E-6 1.828-6 1.34E-6 1.188-6
[Fe“]Out

 

 

58

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table B.2 (Cont'd)

Exp. 6 Exp. 7 Exp. 8 Exp. 9 Exp.10

7.35 2.24 4.13 5.79 6.29

4.47E-8 5.7SE-3 7.41E-5 1.623-6 5.14E-7
2.24E-7 1.74E-12 1.3SE-IO 6.17E-9 1.95E-8l

1.3lE-4 1.252-4 1.158-4 1.21E-4 1.19E-4

2.00E-4 2.00E-4 2.00E-4 2.00E-4 2.00E-4

1.29E-5 1.17E-5 1.17E-5 1.358-5 1.39E-5

----- 3.42E-5 3.42E-5 3.518-5 3.328-5

IIZCO3 4.25E-5 4.808-3 4.77E-3 3.67E-3 2.48E-3

HCO,’ 4.57E-3 4.13E-7 3.088-5 1.13E-3 2.323-3

6.013-6 4.468-15 2.44E-11 4.28E-8 2.653-7

[03] 6.41E-6 3.35E-6 3.27E-6 4.05E-6 4.062-6

[DCB] 2.93E-6 3.7OE-7 4.27E-7 1.38E-6 1.92E-6

[Fe2*] ----- 4.12E-6 4.44E-6 5.79E-6 6.03E-6
MODEL [8202] 7.21E-6 1.27E-5 1.14E-5 3.98E-6 2.58E-6I
OUTPUT [802'] 3.443-10 4.45E-15 4.18E-13 5.62E-12 1.10E-1]]
OR 1.11E-12 1.283-11 1.10E-11 3.32E-12 1.98E-12
'HO, 2.66E-13 4.468-9 «LOSE-11 1.133-124.94E-13
'HO, 3.988-13 8.23E-13 7.86E-13 9.47E-13 8.89E-13l
r_ _ 'I-IO4 3.76E-13 2.25E-12 21.89-12.078-13 4.23E13
EXP. [O3]Out 2.14E-6 1.88E-6 3.9OE-7 9.9OE-7 1.26E-6
RESULT [DCB]Out 2.323-6 4.27E-6 1.38E-6 2.06E-6 2.69E-6
_--IFm°-- 6.392-611.86U1
Note: 1 T e exper men a numbers are sted n Tab e 2.2.

(2) The oxygen concentration is an estimated value in
this work.

59

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

     

 

 

 

  

 

 

 

 

   

 

Table 8.3 The Input/Output Data of Kinetic Model
for Ozone/11202 Treatment System
Exp. No.0) Exp. 1 Exp. 2 Exp. 3 Exp. 4

pH 5.40 6.1 7.28 5.33 6. 01 xp:l

[11+] 3.98E-6 7.94E-7 5.25E-8 4.68E-6 9. 77E-7
[OH‘] 2.51E-9 1.26E-8 1.91E-7 2.14E-9 1. .02E-1

INPUT [03] 1.25E-4 1.20E-4 1.22E-4 1.25E-4 1. 24E-4
DATA [02]“) 2.00E—4 2.00E-4 2.00E—4 2.00E-4 2.00E-il
[DCB] 1.42E-5 1.21E-5 1.21E-5 1.33E-5 9.69E-6
[Fe2+] ------------------------- J

[H202] 6.38E-5 6.23E-5 6.45E-5 6.92E-5 6.35E-5
H2CO3 1.88E-3 1.32E-3 2.12E-4 4.53E-3 3.35E-3l

HCO,‘ 2.21E-4 7.78E-4 1.89E-3 4.65E-4 1.65E-3

__ L L 9°" 3 FLE'9 5-P‘LEL 1. -9_____ 5L {K939
F [03] 4.77E-5 2.73E-5 9.17E-6 4.71E-5 2.70E-5
[DC81 5.083-6 2.74E-6 1 54E-6 4.69E-6 2.29E-6l

, [893+] -------------------------
MODEL [H202] 6.51E-5 5.07E-5 1.65E-5 6.88E-5 4.65E-5
OUTPUT [HOZ'] 3.42E-11 1.34E-10 6.50E-10 3.16E-11 1.02E-1
'OH 7.79E-13 1.43E-12 2.64E-12 7.91E-13 1.32E-12l
'HO2 3.80E-13 3.27E-13 3.64E-13 4.31E-13 Lam-fl
“H03 5.68E-13 7.35E-13 6.47E-13 5.92E-13 8.06E-13
k H04 1.95E-12 2.058-12 1.28E-12 1.96E-12 1.88E12
[O,JOut 2.85E-5 5.22E-6 7.85E-6 3.95E-6 1.35E-6
EXP. [DCBJOut 1.68E-6 1.19E-6 1.32E-6 1.45E-6 1.05E-6

RESULT [Fe2*]0ut -------------------------
[8,0,]Out 5.18E-5 2.95E-5 4.48E-5 2.60E-5

 

 

 

       

 

 

 

 

 

60

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Table 8.3 (Cont'd)
Exp. No.m Exp. 6 Exp. 7 Exp. 8 Exp. 9 Exp.10
pH 7.35 2.24 4.13 5.79 6.29 I
[11*] 4.47E-8 5.75E-3 7.4lE-5 1.62E-6 5. 14E-7l
[OI-f] 2.24E-7 1.74E-12 1.35E-10 6.17E-9 1.95E-d
INPUT [O3] 1.29E-4 1.23E-4 1. l6E-4 1. 19E-4 1.20E-4l
DATA [02] 2 . 00E-4 2 . 00E-4 2 . 00E-4 2 . ODE-4 2 . 00E-4 I
[DCB]m 1.29E-5 1.17E-5 1.17E-5 1.35E-5 1.39E-5l
[Fe2+] ----- 3.42E-5 3.42E-5 3.51E-5 3.328-5]
[H202] 7.28E-5 6.25E-5 5.90E-5 6.66E-5 6.34E-Sl
H2CO3 4 . 25E-5 4 . 80E-3 4 . TIE-3 3 . 678-3 2 . 48E-3
HCO, 4 . 57E-3 4 . 13E-7 3 . 08E-5 l . 13E-3 2 . 32E-3
6.0- 4.46E-15 2.44E_1__8_.2"
[03] 1.17E-5 7.71E-6 6.89E-6 6.07E-6 5.97E-6 .
[DCB] 2 . 50E-6 6 . 65E-7 6 . 61E-7 1 . 19E-6 1 . 69E-6l
[Fez+] ----- 2.64E-6 2.87E-6 3.67E-6 3.93E-6
MODEL [H202] 1 . 17E-5 4 . 96E-5 4 . 48E-5 2 . 68E-5 1 . 45E-5
IOUTPUT‘ [1102’] 5.56E-10 1.74E-14 1.62E-12 3.80E-11 6.20E-1
'OH 1.4SE-12 6.9OE-12 6.94E-12 4.218-12 2.788-12
'HOz 3.75E-13 2.54E-9 2.68E-11 1.37E-12 7.28E-13
'HO3 6.29E-13 1.11E-12 1.088-12 1.33E-12 1.33E-12
'HO4 8.928-13 2.808-12 2.528-12 1.3SE-12 8.4E-31
[O3]Out 4.96E-6 1.42E-5 1.183-6 2.72E-6 2.43E-6
EXP . LDCB] Out 1 . 488-6 ‘7 . 698-6 1 . 918-6 1 . 768-6 2 . DOE-6
RESULT [Fe“]0ut ----- 6.63E—6 8.93E-6 8.87E-6 7.80E-6
[820,] Out 3 . 728-5 2 . 033-5 1 . 4512-5 3 . 66E-5 3 . 80E-5
No e: 1 T e experimenta m

 

 

 

 

 

 

(2) The oxygen concentration is an estimated value in
this work.

APPENDIX C

Ozone, DCB, H202, and Fe2+ Sampling Summary
for Each Experiment

61

EXP. 1 (1/21

11 pH = 5.40
21 [HCO3-l: 0.0021 mole/L
31 Pump Flownu : Ozone = 12.301 mL/min.
DCB = 12.340 mL/min.
NaOH = 0.000 mL/min.
NeHC03 = 0.628 lemin.
H202 = 0.106 mL/min.
4) Hyckullc Retention Time = 9.89 min ( w/o H202 1 9.85 mm ( wl H202 )
51 Volune of The Reactor = 250 mL

Raw Reactor Wt.1 Wt.2 Initial k' Sk'

O . #REF! #REF! #REF! #REFI “EH

2 0.152 123.32 205.11 230.56 49.93 2.37 0.149 0.009
03

226.69

229.59

3 0.155 125.76 206.00 230.54 . . . 3.323 0.509
03!
UV

230.37

226.96

4 0.155 1 25.23 205.85 230.36 . 1 .42
O3! ‘
H202

201 .97 225.80

 

Note : ' weight of beaker only
' ' weight of beaker + indigo blue

 

 

62

EXP. 1 (2121

006 Standard Cellaretion CII'VO

   

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Std. DCB TCB Useful DIT Calibration Curve : Y = 0.05 + 3.11 X
r = 0.9999
1 1 where : X is the DCB/T CB ratio
Y is the DCB concentration 1 ppb 1
Effluent DCB concentration
Exp. DCB TCB Useful DIT DCB Ave. 95% It' Sk'
No. a‘res area Smle uM t! 0.1. (In—514 l 95% 0.1.
1 51008 10897 5 4.6809 14.58 14.23 0.98 0.000 ”W
41773 8941 4.6721 14.56
48325 10122 4.7743 14.87
73637 17833 4.1293 12.87
61111 13339 4.5814 14.28
2 14701 8275 5 1.7766 5.56 5.05 0.51 0.184 0.029
03 28731 19640 1.4629 4.59
25292 15909 1 .5898 4.98
16950 9872 1.7170 5.38
27122 17903 1.5149 4.75
3 4059 19100 5 0.2125 0.71 0.76 0.04 1 .782 0.161
03! 1870 7845 0.2384 0.79
2456 10345 0.2374 0.78
1233 5266 0.2341 0.77
£26 9989 0.2329 0.77
4 5990 10641 5 0.5629 1.79 1 .68 0.16 0.759 0.094
03/ 6395 11419 0.5600 1.79
H202 8488 15793 0.5375 1.72
8545 17112 0.4994 1.60
8853 18954 0.4671 1.50
Calibration Curve Y = -1 2.62 + 162.06 X
r = 0.9996
where: "X" is the UV absorption at 551 nm
'Y" is the concentration of H202 in uM
"r" is the correlation coefficient
H202 Sample
Exp. lnfluent Effluent k' Sk'
Abs. ueraw) uMinitial Ave. 5% CJ Abs. uM Ave. 95% C.|. ( min.-1 1 min.-1
4 0.610 15250 63.70 63.75 0.07 0.396 51.56 51.76 0.26 0.024 0.001
0.610 15250 63.70 0.397 51.72
0.611 15275 63.81 0.396 51.56
0.610 15250 63.70 0.398 51.88
0.611 15275 63.81 0.399 52.05

 

 

63

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EXP. 2 l1/21
1) pH = 6.30
21 (11003-1: 0.0021 mole/L
31 Punp flowrate: Ozone = 12.301 mL/min.
DCB = 12.340 mL/min.
NaOH = 0.278 mL/min.
NaHCO3 = 0.628 mL/min.
H202 = 0.106 mL/min.
41 Hydraulic Retention Time 9.79 minlwio H202) 9.75 min(w/H202)
51 Volume of The Reactor = 250 mL
Ozone Concentration
INFLUENT EFFLUENT
Exp. Raw Reactor Wt.1 Wt.2 Initial Final Ozone Concontration(mgM k' Sk'
Abs. uM fl)” lg)” Abs. Abs. Data ub«Ave Ave. 95%C.I min.-1 min.-1
1 0 0.00 --- -- --- ##IHM ##### ##### ##### ##### #####
m ##1##
-.- ##1##
--- --- --- --- ##MM #####
m ##1##
--- #####
--- -- «- --- ##### #####
--- #####
--- ”##4##
2 0.149 119.57 205.33 231.58 1.008 0.658 28.43 28.56 28.98 1.98 0.319 0.023
03 0.657 28.63
0.657 28.63
201.41 227.13 1.008 0.664 28.47 28.47
0.664 28.47
0.664 28.47
201.83 228.03 1.008 0.651 29.97 29.90
0.652 29.76
0.651 29.97
3 0.15 120.38 204.94 231.38 1.008 0.791 1.25 1.25 1.21 0.26 10.057 2.195
03! 0.791 1.25
UV 0.791 1.25
202.86 230.56 1.008 0.784 1.03 1.09
0.783 1.22
0.784 1.03 .
204.65 230.50 1.008 0.795 1.22- 1.29
0.794 1.43
0.795 1.22
4 0.15 119.88 205.58 231.57 1.008 0.774 5.33 5.26 5.22 0.87 2.255 0.376
03] 0.774 5.33
H202 0.775 5.13
201.25 227.29 1.008 0.776 4.85 4.85
0.776 4.85
0.776 4.85
206.01 232.22 1.008 0.772 5.41 5.54
0.771 5.61
0.771 5.61
Note : ' weight of beaker only

weight of beaker + indigo blue

 

008 Standard Cellaretion Cave
DCB

Std.

0.00

Effluent 008 concentration

0

1

TCB
17893
1 1005

7

97

11

11

Useful

D

0.00

 

64

EXP. 2 (2l21

Calibration Curve :

Y

I .-

0.11

0.9987

+

where : X is the DCB/TCB ratio

3.15

Y is the DCB concentration ( ppb )

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

X

 

 

 

Exp. DCB TCB Useful DIT DCB Ave. 95% k' Sk'
No. area area Sajmgle uM fl C.l. (min-1 1 95% 0.1.J
1 33689 8339 4 4.04 12.85 12.14 0.79 0.000 #DIVIOI

37205 9802 3.80 12.08
44590 11915 3.74 11.91
29938 7075 4.23 13.46
44866 12198 3.68 11.71
2 17379 11121 4 1.56 5.04 5.09 0.29 0.142 0.019
03 17510 11346 1.54 4.98
19555 12674 1.54 4.98
15316 9216 1.66 5.35
9064 4645 1.95 _6._27
3 3319 7983 4 0.42 1.42 1 .38 0.07 0.795 0.071
03/ 3044 7685 0.40 1.36
UV 4593 11886 0.39 1.33
3953 9584 0.41 1 .41
2647 5819 0.45 1 .55
4 2055 5462 4 0.38 1 .30 1.19 0.07 0.943 0.088
03/ 3165 9326 0.34 1.18
H202 2688 7570 0.36 1.23
3089 8855 0.35 1.21
3397 10500 0.32 1.13
Calibration Curve Y = -11.87 + 170.05 X
r = 0.9995
where ; "X" is the UV absorption at 551 nm
"Y' is the concentration of H202 in uM
"r" is the correlation coefficient
H202 Semw
Exp. lnfluent Effluent k' Sk'
Abs. uMiraw) uMinitia Ave. 5% OJ Abs. u_M_ Ave. 95% C.l. (m_i_n.-1 1 min.-1
4 0.603 15075 62.29 62.29 0.00 0.296 38.46 38.53 0.12 0.063 0.000
0.603 15075 62.29 0.297 38.63
0.603 15075 62.29 0.296 38.46
0.603 15075 62.29 0.296 38.46
0.603 15075 642.23 (L297 38.63

 

 

 

 

 

 

 

 

 

 

 

 

65

EXP. 3 l1l21
11 PH = 7.28
21 [HOO3-l= 0.0021 mole/L
31 Punp flowrate : Ozone = 12.301 mL/min.
DCB = 12.340 lemin.
NaOH - 0.000 mL/min.
NaHCO3 = 0.628 mL/min.
H202 = 0.106 mL/min.
41 Hydraulic Retention Time 9.89 min i wlo H202 1 9.85 min ( w/ H202 1
51 Volune of The Reactor = 250 mL

Ozone Concentration

Exp. Raw Reactor Wt.1 Wt.2 Initial k'

I.

1 0 . #### ##### ##### ##### #####

#

2 0.152 123.32 203.04
03

3 0.152 123.32 202.62 . 3.86 3.69 0.37 3.277 0.333
03!

UV

0.31 1 .477 0.059

230.71

 

Note : ’ weight of beaker only
' ' weight of beaker + indigo blue

66

 

 

 

 

 

 

 

EXP. 3 (2/21
Useful DIT
Calibration Curve : Y = 0.25 + 3.20 X
r = 0.9990
where : X is the DCBIT CB ratio
Y is the DCB concentration ( ppb 1
Effluent DCB concentration
—E‘xp. DCB TCB Useful DIT oca Average 95% k' Sk'
No. area area Smle uM I! 0.1. ( min-1 1 95% 0.1.
1 72324 20067 4 3.60 1 1.80 12.09 0.69 0.000 #DlV/Ol
73233 20530 3.57 1 1.68
55144 13544 4.07 13.30
65701 17527 3.75 12.26
59308 15355 3.86 12.63
2 31805 20660 4 1.54 5.18 5.96 0.23 0.104 0.013
03 22859 12463 1 .83 6.13
26563 15369 1.73 5.79
23703 13379 1.77 5.93
M3 1 1569 1.80 6.02
3 8980 19392 4 0.46 1.73 1.82 0.12 0.571 0.055
03! 8223 17267 0.48 1 .78
UV 7187 14032 0.51 1.89
6035 10893 0.55 2.02
8227 1_6209 0.51 1 .88
4 5765 20193 4 0.29 1.16 1.32 0.12 0.828 0.095
03/ 3687 10782 0.34 1.35
H202 5742 19233 0.30 1.21
3123 8854 0.35 1.38
4270 L241 7 0.34 1.35

 

 

 

 

 

 

 

 

 

 

 

 

 

Calibration Curve Y a -10.33 + 165.32 X
r = 0.9994
where ; "X' is the UV absorption at 551 nm
'Y" is the concentration of H202 in uM
"r' is the correlation coefficient

 

 

 

 

H202 Semge
Exp. lnfluent Effluent k' Sk‘

_A£s. quaw uMinitia Ave. 5% C.l Abs. l._l_M Ave. 95% 0.1. ( min.-1 1 min.-1
4 0.616 15400 64.33 64.46 0.14 0.242 29.67 29.54 0.47 0.120 0.003

0.617 15425 64.44 0.238 29.01

0.617 15425 64.44 0.244 30.00

0.617 15425 64.44 0.240 29.34

0.619 15475 64.64 0.242 __29.67

 

 

 

 

 

 

 

 

 

 

 

 

 

11 pH = 5.40

21 [11003-1 =

31 Punp flowrate :

41 Hydraulic Retention Time

51 Volume of The Reactor =

Ozone Concenuation

Ozone

NaOl-l
Fa(|l1
H202 =

0.0048 mole/L

DCB

9.78 min ( w/o H202 1

67

EXP. 4 (1/21

12.301
12.340
0.930
0.000
0.106

250 mL

mL/min.
mL/min.
mL/min.
mL/min.
mL/min.

9.74 min ( w/ H202 1

 

Exp.

lNFLUENT

EFFLUENT

 

Raw
Abs.

Reactor

uM

Initial
Abs.

Final
Abs.

Ozone Concr

 

intration i uM 1

 

Data

ub-Ave

Ave.

95%C.I

kl
min.-1

Sk'
min.-1

 

 

1

0

0.00

#####

 

#####

 

#####

#####

 

##1##

 

##1##)?

 

#####

#####

 

#####

 

#####

 

#####

#####

#####

#####

#####

#####

 

03

0.156

1 25.07

205.44

234.71

0.995

29.54

 

29.36

 

29.54

29.48

 

202.70

228.74

0.995

30.70

 

30.70

 

30.70

30.70

 

201.93

235.82

0.995

29.66

 

29.66

 

29.66

29.66

29.95

1.63

0.325

0.01 9

 

03/
UV

0.157

1 25 .88

205.99

231.75

1.001

 

.44

.23

 

.44

1.37

1 .56

 

201.29

227 .22

1.001

.62

 

 

.82

32‘

1.75

 

201.71

227.38

1.001

.56

 

d—b-l—D—A—h-J-L

.56

 

_.e

.56

1.56

0.48

8.152

2.502

 

03/
H202

 

0.157

 

1 25.36

204.98

232.82

0.999

4.09

 

3.71

 

3.90

3.90

3.“

 

205.48

231.11

0.999

3.98

 

3.98

 

3.98

3.98

 

 

202.18

 

227.82

 

0.999

3.97

 

3.97

 

 

 

3.97

 

3.97

 

0.10

 

 

3.157

 

0.081

 

Note : ’

weight of beaker only
weight of beaker + indigo blue

 

68

 

 

 

 

 

 

 

EXP. 4 l2/21
Std. DCB TCB Useful DIT Calibration Curve : Y - -0.12 + 3.51 X
r a 0.9999
7 where : X is the DCB/T CB ratio
70 10003 18741 Y is the DCB concentration ( ppb 1
4 1 1
5
13 7065
1
7
71
Effluent DCB concentration
Exp. DCB TCB Useful DIT DCB Ave. 95% k' Sk'
No. a_rea area Sample uM 1L4 C._l. ( min-1 95% 0.1.1
1 91354 23201 4 3.9375 13.68 13.30 0.45 0.000 #DlVlOl
91234 23796 3.8340 13.32
85706 20571 4.1664 14.49
100834 26926 3.7449 13.01
103% 27196 3.7962 13.19
2 50801 2601 1 5 1.9531 6.73 6.54 0.28 0.106 0.010
03 53864 28185 1.9111 6.58
52372 28590 1.8318 6.30
43194 21906 1.9718 6.79
51340 27984 1.8346 6.31
3 10870 25737 4 0.4223 1.36 1 .34 0.08 0.910 0.063
03] 10007 22929 0.4364 1.41
UV 8724 19670 0.4435 1.43
9883 24329 0.4062 1 .30
10850 26479 0.4098 1.31
4 10084 22286 4 0.4525 1.46 1 .45 0.15 0.839 0.094
03/ 1 1662 27299 0.4272 1 .37
H202 12188 28339 0.4301 1 .38
5070 9157 0.5537 1 .82
8908 18318 0.4863 1.58

 

 

 

 

 

 

 

 

 

 

 

 

 

Calibration Curve Y = -11.43 + 197.87 X
r - 0.9998
where ; "X" is the UV absorption at 551 nm
'Y' is the concentration of H202 in uM
'r" is the correlation coefficient

 

 

 

 

H202 Sample
Exp. lnfluent Effluent k' Sk'

Alba. ueraw) uMinitia! AverageES% C.l __A_l_)s. uM Average 95% 0.1. “rim-1 1 min.-1
4 0.669 16725 69.04 69.17 0.11 0.281 44.17 44.84 0.51 0.056 0.001

0.670 16750 69.15 0.285 44.96

0.671 16775 69.25 0.286 45.16

0.671 16775 69.25 0.284 44.76

0.670 16750 69.15 0.286 45.16

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

69

EXP. 5 l1/21

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

11 pH = 6.01
21 [HCO3-1= 0.0048 mole/L
31 Punp Flowrate: Ozone = 12.301 mL/min.
DCB = 12.340 mL/min.
NaOH = 1.205 mL/min.
Fe(II) = 0.000 mL/min.
H202 = 0.106 mL/min.
41 Hyfiadic Retention Time 9.67 min ( w/o H202 ) 9.63 min ( wl H202 1
51 Volune of The Reactor = 250 mL
Ozone Concentration
INFLUENT IEFFLUENT
Exp. Raw Reactor Wt. 1 Wt. 2 initial Final Ozone Concentration ( uM) k' Sk'
Abs. uM (91’ (91” Abs. Abs. Data ub-Ave Ave. 5% C.l min.-1 min.-1
1 0 0.00 --- --- --- --- ##1##! ##### ##### ##### ##### #####
-~- #####
--- #####
-- --- -- --- ##### #####
--- ##1##
--- #####
--- --- --- ##### #####
--- #####
--- #####
2 0.154 122.16 201.58 227.56 1.000 0.655 28.39 28.46 29.37 2.30 0.327 0.027
03 0.654 28.59
0.655 28.39
205.88 232.08 1.000 0.648 29.29 29.36
0.648 29.29
0.647 29.49
205.69 231.75 1.000 0.644 30.44 30.31
0.645 30.24
0.645 30.24
3 0.156 123.74 201.62 228.77 1.000 0.780 1.27 1.27 1.28 0.20 9.869 1.513
03/ 0.780 1.27
UV 0.780 1.27
206.26 232.37 1.000 0.787 1.21— 1.21
0.787 1.21
0.787 1.21_
203.32 230.08 1.000‘ 0.782 1.37 1.37'
0.782 1.37
0.782 1.37
4 0.157 124.03 204.79 228.36 1.000 0.803 1.41 1.41 1.35 0.47 9.434 3.310
03] 0.803 1.41
H202 0.803 1.41
202.19 224.33 1.000 0.814 1.14 1.14
0.814 1.14
0.814 1.14
204.87 229.81 1.000 0.793 1.57 1.50
0.793 1.57
0.794 1.36
Note: ’ weight of beaker only

weight of beaker + indigo blue

 

70

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EXP. 5 (ZIZl
Useful DIT Calibration Curve : Y = -0.01 + 3.13 X
r = 0.9984
where : X is the DCB/'1' CB ratio
Y is the DCB concentration ( ppb 1
Effluent DCB concentration
Exp. DCB TCB Useful DIT DCB Ave. 95% lt' Sk'
No. _area area $a_rr_igle uM it“ 0.1. mh-1 95% C.l.1
1 - - 4 ###### ##### 9.69 0.33 0.000 #DlV/Ol
44265 14541 3.0442 9.50
44448 13941 3.1883 9.95
45373 14826 3.0604 9.55
43567 13951 3.1229 9.75
2 18946 12359 5 1.5330 4.78 4.71 0.16 0.109 0.009
03 19138 12477 1.5339 4.78
18631 12708 1.4661 4.57
19661 13411 1.4660 4.57
17609 11325 1.5549 4.85
3 5350 14067 5 0.3803 1.18 1.18 0.02 0.746 0.032
03! 5208 13700 0.3801 1 .18
UV 5095 13522 0.3768 1 .17
4684 11976 0.3911 1.21
5125 13567 0.3778 1.17
4 4700 14181 4 0.3314 1 .02 1 .05 0.03 0.858 0.042
03! 4760 13743 0.3464 1 .07
H202 4461 13072 0.3413 1 .05
4692 15053 0.31 17 0.96
4081 12176 0.3352 1.04
Calibration Curve Y a -12.79 4» 168.56 X
r = 0.9998
where ; 'X' is the UV absorption at 551 nm
"Y" is the concentration of H202 in uM
'r" is the correlation coefficient
H202 Sam
Exp. lnfluent Effluent k' Sk'
Abs. uMiraw) uMinitia Ave. 5% C.l Abs. _gM Ave. 95% 0.1. ninsl min.-1
4 0.622 15550 63.51 63.51 0.00 0.227 25.47 26.01 0.58 0.150 0.004
0.622 15550 63.51 0.229 25.81
0.622 15550 63.51 0.229 25.81
0.622 15550 63.51 0.232 26.31
0.622 15550 63.51 0.234 26.65

 

 

 

11 pH = 7.35

21 (11003-1 =

31 Pump Flowrate :

Ozone

41 Hydratlic Retention Time

NaOl-l

H202

0.0050 mole/L

DCB

Fe(II)

10.15 min ( wlo H2021

71

EXP. 6 (1/21

12.301
12.340
0.000
0.000
0.106

mL/min.
mL/min.
mL/min.
mL/min.
mL/min.

10.10 min ( w/ H2021

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

51 VoltaneofTtheactor: 250 mL
Ozone Concentration
INFLUENT EFFLUEN‘iF
Exp. Raw Reactor Wt.1 VVt.2 Initial Final Ozone ConcuntrationiuM) k' Sk'
Abs. UN! (91' fl)" Abs. Abs. Data ub—Avew Ave. 5% 0.1 min.-1 min.-1
5 0 0.00 —-- -- --- --- ##1## ##### ##### ##### ##### #####
--- #####
--- #####
--- -- ~-- -- ##### #####
m ##1##!
m ##1##!
--- --- --- --- ##1##” #####
--- #####
--- #####
2 0.157 130.63 202.28 227.22 0.993 0.614 38.52 38.52 37.41 2.52 0.246 0.018
03 0.614 38.52
0.614 38.52
204.54 229.41 0.993 0.621 37.23 37.16
0.622 37.02
0.621 37.23
205.19 230.13 0.993 0.623 36.61 36.53
0.624 36.39
0.623 36.61
3 0.157 130.63 205.63 230.36 0.992 0.786 2.00 1.93 2.14 0.45 5.913 1.256
03] 0.787 1.79
UV 0.786 2.00
201.28 225.97 0.993 0.786 2&1 2.23
0.786 Lg.
0.786 2.23
204.93 229.63 0.992 0.785 2.26 2.26
0.785 2.26—
0.785 2.26
4 0.156 129.24 204.77 229.63 0.992 0.771 5.1; 5.02 4.96 0.23 2.479 0.115
03! 0.771 522_
H202 0.771 5.02
204.99 230.04 0.992 0.769 5.15 5.01
0.770 4.94
0.770 4.94
205.84 230.99 0.992 0.769 5.00 4.86
0.770 4.79
0.770 4.79
Note : ‘ weight of beaker only

00

weight of beaker + indigo blue

 

72

EXP. 6 (2/21

Useful

DIT

Calibration Curve :

20.41
27.21

Effluent DCB concentration

0
1
611

1 64
65246984

108918464

1
1
1

5
12855284
16399562

1

0
0.8383
1 .6963

5.0755
6.641

 

Y-

f =

-0.12
0.9997

+

4.07

where : X is the DCB/T CB ratio
Y is the DCB concentration ( ppb 1

X

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

  

 

 

Exp. DCB TCB Useful DIT DCB Ave. 95% k' Sk'
No. area area Sample uM tfl 0.1. ( mh-1 1 95% 0.11
5 42310060 13319260 3 3.1766 12.80 12.88 1 .62 0.000 #DlVlOl
35035196 10408399 3.3661 13.57
32171084 9067013 3.5481 14.31
50737080 16653456 3.0466 12.27
26554630 7467993 3.5558 14.34
2 25871216 7000310 3 3.6957 14.91 6.83 1 .58 0.087 0.038
03 7794684 3598859 2.1659 8.69
18995326 10096146 1.8814 7.53
25777322 16350205 1.5766 6.29
22220724 13320606 1.6681 6.66
3 9278464 16309450 5 0.5689 2.19 2.32 0.1 9 0.449 0.079
03/ 8017264 12561038 0.6383 2.47
UV 9193751 15429505 0.5959 2.30
8865530 15819229 0.5604 2.16
6791351 10600781 0.6406 2.48 _
4 5895520 1651 6268 4 0.3570 1 .33 1 .48 0.33 0.765 0.203
03/ 481 1330 10282525 0.4679 1.78
H202 6521023 16987228 0.3839 1 .44 4
6082735 16640806 0.3655 1.36
3091237 103559 29.8500 121.34
H202 CaIbration Crave
Std.
Calibration Curve Y = -10.94 + 180.02 X
r = 0.9998
where ; ”X" is the UV absorption at 551 nm
”Y" is the concentration of H202 in uM
'r" is the correlation coefficient
H202 Sam
Exp. _ lnfluent Effluent k' Sk'
_Abs. uM(raw1 uMinitia . Abs. uM Ave. 95% C.l. Lmin.-1 1 min.-1
4 0.677 16925 72.50 0.28 0.174 20.39 19.16 1 .02 0.277 0.016
0.682 17050 73.03 0.162 18.23
0.680 17000 72.82 0.166 18.95
0.678 16950 72.60 0.169 19.49
0.681 17025 72.92 0.165 18.77

 

 

 

 

 

 

 

 

 

 

 

 

73

EXP. 7 (1/31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

11 pH = 2.24
21 (11003-1: 0.0048 mole/L
31 Pump flowrate : Ozone = 12.301 mL/min.
DCB = 12.340 rnL/min.
NeOH = 0.000 mL/rnin.
Fe(ll) = 0.984 mL/min.
H202 = 0.106 mL/min.
41 Hydredic Retention Time 9.76 min ( wlo H202 1 9.72 min ( w/ H202 1
51 Volume of The Reactor = 250 mL
Ozone concentration 1
INFLUENT EFFLUENT
Exp. Raw Reactor Wt. 1 Wt. 2 Initial Final Ozone Concentration ( uM 1 k' Sk'
Abs. uM (91' (g 1" Abs. Abs. Data ub-Ave Ave. 5%C.l min.-1 min.-1
1 0 0.00 --- --- -- --- ##### ##### ##### ##### ##### #####
«- #####
--- ##1##
--- --— -- -- ##### #####
-- #####
--- #####
-- -- -- -- ##### #####
«- #####
-- #####
2 0.158 126.41 205.51 230.57 1.037 0.601 48.40 48.33 48.55 0.91 0.164 0.004
03 0.602 48.18
0.601 48.40
205.64 230.55 1.037 0.601 48.90 48.97
0.601 48.90
0.600 49.1 1
202.47 234.66 1.037 0.491 48.45 48.34
0.492 48.29
0.492 48.29
3 0.156 124.81 201.69 227.52 1.030 0.810 1.76 1.76 1.88 0.29 6.710 1.027
03! 0.810 1.76
UV 0.810 1.76
205.86 231.43 1.030 0.811 1.92 1.99
0.81 1 1 .92
0.810 2.13
202.39 228.43 1.030 0.808 1.88 1.88
0.808 1.88
0.808 1.88
4 0.154 122.70 201.09 226.89 1.039 0.758 13.99 13.99 14.16 0.39 0.789 0.022
03! 0.758 13.99
H202 0.758 13.99
201.77 227.84 1.039 0.754 14.30 14.30
0.754 14.30
0.754 14.30
201.75 228.71 1.039 0.747 14.07 14.20
0.746 14.27
0.746 14.27
Note : ' weight of beaker only

00

weight of beaker + indigo blue

 

 

74

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EXP. 7 (2I31
008 8w Calliration Ora-vs
Std. DCB TCB Useful DIT Ave.
uM area area Sample 1 ppb 1
0.00 0 10994926 1 0.0000
0.68 2709133 15521120 3 0.1745 0.1703
2822517 16987612 0.1662
2745956 16142584 0.1701
1.70 6871543 16668120 3 0.4123 0.4096
6875499 16747235 0.4105
6690765 16485668 0.4059
3.40 13057246 15762961 3 0.8283 0.8130
13367006 16621329 0.8042
12637938 15671754 0.8064
5.10 19683484 16073414 3 1.2246 1 .2240
18523668 15070709 1 .2291
19661632 16137345 1.2184
6.80 21615140 14528687 3 1.4878 1.4871
. 22855978 15308210 1.4931
2431 3048 1 6422267 1 .4805
13.61 51689228 15674178 3 3.2977 3.2538
51457456 15652338 3.2875
52288980 16463539 ‘ 3.1760
Calibration Curv Y = 0.03 + 4.22 X

r 0.9989
where : X is the DCB/TCB ratio
Y is the DCB concentration ( ppb 1

Effluent 008 concentration

 

 

 

 

 

 

Exp. DCB TCB Useful 071" DCB Ave. 95% k' Sk'
No. area area Sample uM 1" OJ. (mm-1 1 95% 0.1.
1 46946456 18051014 5 2.6009 11.01 11.66 1.00 0.000 #DIVIOI

44066540 17263168 2.5538 10.81

42161780 15532214 2.7145 11.49

33547360 11236201 2.9856 12.63

34653944 11895535 2.9132 12.33
2 29263926 11315878 5 2.5879 10.96 10.01 0.67 0.017 0.012
03 41260608 18137916 2.2748 9.63

37601592 16059582 2.3414 9.92

42656566 18578544 2.2960 9.72

41933352 18087354 2.3184 9.62
3 12474441 12833113 3 0.9721 4.14 4.27 0.35 0.177 0.029
03/ 1 1479692 1 1060421 1.0379 4.41
uv 12059614 12036641 1.0019 4.26

9626623 91 17885 1.0560 4.49

10364590 9726083 1 .0656 4.53
4 25355524 13672650 3 1.8545 7.66 7.69 0.41 0.053 0.015
03/ 29374664 16242061 1 .6066 7.67
H202 19809200 9844410 2.0122 8.53

16262672 8638766 2.0665 8.76

32074566 18055012 1 .7765 7.53

 

 

 

 

 

 

 

 

 

 

 

75

EXP. 7 (3/31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Effluent Foill1
Exp. Sample Measured with 10 cm cell Fe(II) conc. ( uM 1 k' Sk'
No. Abeorbance Ave. Effluent Ave. 95% C.l. (min-1 1 (min-1 1
1 1 1.9736 1.9745 1.9704 1.9728 34.02 34.21 0.40 0.000 #DlV/Ol
2 1.9936 1.9895 1.9846 1.9892 34.31
3 1.9879 1.9879 1.9902 1.9887 34.30
2 1 0.2215 0.2212 0.2216 0.2215 3.71 3.93 1.11 0.789 0.225
03 2 0.2192 0.2175 0.2156 0.2174 3.64
3 0.2636 0.2645 0.2637 0.2640 4.45
3 1 0.4024 0.4018 0.4017 0.4020 6.83 6.89 0.15 0.406 0.011
03IUV 2 0.4108 0.4079 0.4081 0.4089 6.96
3 0.4045 0.4051 0.4066 0.4054 6.89
4 1 0.3888 0.3900 0.3906 0.3898 6.62 6.63 0.03 0.428 0.007
03/H202 2 0.3910 0.3900 0.3891 0.3900 6.63
3 0.3907 0.3911 0.3918 0.3912 6.65
Calibration Curve : Y = 6.88 + 969.27 X
r = 0.9998
"X" is the value of Absorbance
'Y" is the Fe(II) concentration ( ppb 1
"r' is the correlation coefficient
H202 Calibration Cave
Std. Measruements
uM test 1 test 2 test 3 test 4 test 5 Ave. 95% C.l.
0 0.072 0.074 0.065 0.068 0.067 0.069 0.0046
10 0.100 0.099 0.111 0.098 0.119 0.105 0.0115
25 0.177 0.164 0.165 0.165 0.173 0.169 0.0073
50 0.287 0.300 0.287 0.303 0.293 0.294 0.0091
75 0.417 0.429 0.427 0.421 0.427 0.424 0.0062
100 0.544 0.554 0.547 0.542 0.551 0.548 0.0061
Calibration Curve : Y - -11.81 + 205.62 X
r - 0.9991
where ; 'X" is the UV absorption at 551 nm
'Y' is the concentration of H202 in uM
”r' is the correlation coefficient
H202 Sample
Exp. lnfluent Effluent k' Sk' 1
Abs. uM (raw) M (initia Ave. 95% 0.1. Abs. uM Ave. 95% 0.1. ( min.-1 ( min.-1 1
4 0.606 15150 62.41 62.51 0.13 0.149 18.82 20.26 1.65 0.215 0.019
0.608 15200 62.62 0.165 22.11
0.608 15200 62.62 0.152 19.44
0.607 15175 62.51 0.160 21.08
0.606 15150 62.41 0.154 19.85

 

 

 

 

 

 

 

 

 

 

 

 

 

 

76

EXP. 8 ”/31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

11 pH = 4.52
21 [HCO3-l= 0.0045 mole/L
31 Punp Flowrete : Ozone = 12.301 mL/min.
DCB = 12.340 mL/min.
NaOH = 1.529 mL/min.
Fe(II) = 0.984 mL/min.
H202 = 0.106 mL/min.
41 Hyckedic Retention Time 9.21 min ( w/o H202 1 9.17 min ( w/ H202 1
51 Volune ofThe Reactor = 250 mL
Ozone Concenvetion
INFLUENT EFFLUENT
Exp. Raw Reactor Wt. 1 Wt. 2 Initial Final Ozone Concentration ( uM 1 k' Sk'
Abs. uM (g)' (g 1” Abs. Abs. Data ub-Ave Ave. 195%C.l min.-1 min.-1
1 0 0.00 --- --- --- -- ##### ##### ##### ##### ##### #####
--- #####
-—- ##1##
--~ -- -.. --. ##### #####
..- #####
--- #####
«- -.. -- -- ##### #####
-- #####
--- #####
2 0.152 114.76 205.56 232.94 1.038 0.757 11.24 11.11 11.15 0.52 1.010 0.048
03 0.758 1 1 .04
0.758 11.04
200.95 228.46 1.038 0.757 11.02 10.96
0.758 10.83
0.757 11.02
204.89 232.07 1.038 0.758 11.37 11.37
0.758 1 1 .37
0.758 11.37
3 0.153 115.52 205.11 230.80 1.038 0.824 0.38 0.38 0.39 0.03 32.351 2.716
03/ 0.824 0.38
UV 0.824 0.38
204.07 232.90 1.038 0.804 0.32 0.38
0.803 0.50
0.804 0.32
201.97 228.86 1.038 0.816 0.40 0.40
0.816 0.40
0.816 0.40
4 0.154 115.82 200.93 228.36 1.039 0.810 1.04 1.04 1.18 0.33 10.565 2.938
03/ 0.810 1.04
H202 0.810 1.04
202.59 230.18 1.039 0.808 1.22 1.22
0.808 1.22
0.808 1.22
202.94 230.12 1.039 0.811 1.16 1.29
0.810 1.36
0.810 1.36
Note : ' weight of beaker only

weight of beaker + indigo blue

 

 

 

77

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EXP. 8 (2/31
008 Standard Calibration Owe
Std. 008 TCB Useful DIT Ave.
uM area area Sample
0.00 0 10994926 1 0.0000
0.68 2709133 15521120 3 0.1745 0.1’70_3
2822517 16987612 0.1662
2745956 16142584 0.1701
1.70 6871543 16668120 3 0.4123 0.4096
6875499 16747235 0.4105
6690765 16485668 0.4059
3.40 13057246 15762961 3 0.8283 0.8130
13367006 16621329 0.8042
12637938 15671754 0.8064
5.10 19683484 16073414 3 1.2246 1.2240
18523668 15070709 1 .2291
19661632 16137345 1.2184
6.80 21615140 14528687 3 1.4878 1 .4871
22855978 15308210 1.4931
24313048 1 6422267 1 .4805
13.61 51689228 15674178 3 3.2977 3.2538
51457456 15652338 3.2875
52288980 16463539 3.1760
Calibrat Y a + 4.22 X
r = 0.9989
where : X is the DCB/TCB ratio
Y is the DCB concentration 1 ppb 1
Effluent DCB concentration 4
Exp. DCB TCB Useful DIT DCB Ave. 95% k' Sk'
No. area area Sample uM i“ 0.1. l mh—1 l 95% 0.1.
1 46948456 18051014 5 2.6009 1 1.01 1 1 .66 1 .00 0.000 #DIVIOl
44086540 17263168 2.5538 10.81
42161780 15532214 2.7145 11.49
33547360 11236201 2.9856 12.63
34653944 11895535 2.9132 12.33
2 10695460 14018641 3 0.7629 3.25 3.22 0.50 0.284 0.058
03 8598244 10757099 0.7993 3.41
12720079 18039950 0.7051 3.01
6632140 8077623 0.821 1 3.50
6355219 7226741 0.8794 3.75
3 3203340 9532392 3 0.3360 1 .45 1 .38 0.17 0.808 0.128
03/ 4496051 14806956 0.3036 1 .32
UV 2885068 8505703 0.3392 1 .47
3107331 8633446 0.3599 1.55
4323156 13636830 0.3170 1.37
4 6938908 161 13692 4 0.4306 1 .85 1 .91 0.16 0.566 0.075
03/ 6798474 15514129 0.4382 1 .88
H202 4986220 10354560 0.4815 2.07
6581 630 1 5290490 0.4304 1 .85
3991012 7607872 0.5246 2.25

 

 

 

 

 

 

 

 

 

 

 

 

78

EXP. 8 (3/31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Effluent Fell"
Exp. Sample Measured with 10 cm cell Fe(ll) conc. ( uM 1 k' Sk'
Number Absorbance Ave. Effluent Ave. 95% C.l. (min-1 1 (min-1 1
1 1 1.9736 1.9745 1.9704 1.9728 34.02 34.21 0.40 0.000 #DIVIOI
2 1.9936 1.9895 1.9846 1.9892 34.31
3 1.9879 1.9879 1.9902 1.9887 34.30
2 1 0.4858 0.4836 0.4832 0.4842 8.26 8.18 0.17 0.346 0.009
03 2 0.4771 0.4769 0.4768 0.4769 8.13
3 0.4779 0.4786 0.4768 0.4778 8.15
3 1 0.4227 0.4210 0.4195 0.4211 7.17 7.14 0.05 0.411 0.007
03/UV 2 0.4196 0.4198 0.4201 0.4199 7.14
3 0.4184 0.4187 0.4188 0.4186 7.12
4 1 0.5221 0.5213 0.5208 0.5214 8.90 8.89 0.11 0.310 0.006
03/H202 2 0.5181 0.5179 0.5183 0.5181 8.84
3 0.5230 0.5233 0.5234 0.5232 8.93
Calibration Curve : Y = -6.88 + 969.27 X
r = 0.9998
'X' is the value of Absorbance
'Y' is the Fe(II) concentration ( ppb 1
"r' is the correlation coefficient
H202 Calibration Cuve
Std. Measruements
uM test 1 test 2 test 3 test 4 test 5 Ave. 95% C.l.
0 0.072 0.074 0.065 0.068 0.067 0.069 0.0046
10 0.100 0.099 0.111 0.098 0.119 0.105 0.0115
25 0.177 0.164 0.165 0.165 "0.173 0.169 0.0073
50 0.287 0.300 0.287 0.303 0.293 0.294 0.0091
75 0.417 0.429 0.427 0.421 0.427 0.424 0.0062
100 0.544 0.554 0.547 0.542 0.551 0.548 0.0061
Calibration Curve : Y = -11.81 + 205.62 X
r -= 0.9991
where ; "X" is the UV absorption at 551 nm
"Y' is the concentration of H202 in uM
"r" is the correlation coefficient
H202 Sample
Exp. lnfluent Effluent k' Sk' ]
Abs. uM (raw) M (initial Ave. 95% C.I. Abs. uM Ave. 95% C.l. ( min.-1 ( min.-1 1
4 0.606 15150 58.91 59.01 0.12 0.129 14.71 14.51 0.68 0.335 0.016
0.608 15200 59.10 0.125 13.89
0.608 15200 59.10 0.127 14.30
0.607 15175 59.01 0.127 14.30
0.606 15150 58.91 0.132 15.33

 

 

 

 

 

 

 

 

 

 

 

 

 

 

79

EXP. 9 (1/31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

11 pH = 5.79
21 [11003.]: 0.0047 mole/L
31 Pump Flowretae: Ozone = 12.301 mL/min.
DCB = 12.340 mL/min.
NaOH = 0.890 mL/min.
Fe(II) = 0.990 mL/min.
H202 = 0.106 mL/min.
41 Hyhtdic Retention'l'ime 9.43 minlwlo H2021 9.39 minlw/H2021
51 Volune ofThe Reactor = 250 mL
Ozone Concentration
INFLUENT EFFLUENT
Exp. Raw Reactor Wt.1 Wt.2 Initial Final Ozone ConcentrationluM) k' Sk'
Abs. uM (91* lg)” Abs. Abs. Data ub-Ave Ave. 5%C.l min.-1 min.-1
1 0 0.00 -- -- --- --- ##### ##### ##### ##### ##### #####
--- #####
--- #####
--- --- --- --- ##1## #####
-—- #####
-- #####
--- --- --- -.. ##### #####
--- ##1##
-— ##1##
2 0.157 121.37 204.47 231.17 0.999 0.729 11.84 11.84 11.67 0.36 0.997 0.031
03 0.729 11.84
0.729 11.84
205.05 231.89 0.999 0.729 11.60 11.60
0.729 11.60
0.729 11.60
202.48 229.50 0.999 0.727 11.70 11.57—
0.728 11.50
0.728 11.50
3 0.156 120.69 202.01 228.69 0.999 0.784 0.92 0.85 0.99 0.31 12.763 3.990
03! 0.784 0.92
UV 0.785 0.72
205.14 232.18 0.999 0.781 1.05 1.05
0.781 1.05
0.781 1.05
205.58 232.29 0.999 0.783 1.08 1.08
0.783 1.08
0.783 1.08
4 0.155 119.34 201.35 228.65 0.997 0.769 2.76 776 2.72 0.13 4.666 0.224
03! 0.769 2.76
H202 0.769 2.76
205.20 231.98 0.997 0.773 2.66 2.66
0.773 2.66
0.773 2.66
202.45 229.27 0.997 0.772 2.80 2.74
0.773 2.61
0.772 2.80
Note : ' weight of beaker only

weight of beaker + indigo blue

 

 

 

80

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EXP. 9 (2I31
008 Standard Callaration Cleve
Std. oce 708 Useful on— Ave.
uM area area Sample 1 PPP 1
0.00 0 9551421 1 0.0000
3.40 10036036 1 1407443 2 0.8798 0.8650
8895539 9228770 0.9639
14282330 16798820 0.8502
6.80 13173816 6448658 2 2.0429 1.7416
20498668 1 1226094 1.8260
25515856 15395904 1 .6573
13.61 20705164 5122005 3 4.0424 4.0592
21243764 4984935 4.2616
27279174 7042437 3.8735
20.41 50480372 9043517 3 5.5819 5.5102
48600912 8567202 5.6729
62546984 1 1855284 5.2759
27.21 102418464 16399562 2 6.2452 6.7071
32029644 4050721 7.9071
77318960 10785319 7.1689
Calibration Curv Y - -0.12 + - 4.07 X
r - 1 .0000
where : X is the DCB/T CB ratio
Y is the OCR concentration ( ppb 1
Effluent 008 concentration
Exp. DCB TCB Useful DIT DCB Ave. 95% k' Sk'
No. area area Sample uM 1M C.l. ( mh-1 l 95% 0.1.
1 41 524576 1 2620246 3 3.2903 1 3.267 1 3.48 0.54 0.000 #DlVlOl
39617216 1 1660055 3.3977 13.704
43614064 630162 69.2109 281.6
19532540 5073315 3.8501 15.545
44010712 13177716 3.3398 13.469
2 10319936 9593831 3 1.07537 4.26 4.35 0.19 0.223 0.017
03 7386303 6291530 1 .1740 4.66
8777255 7897060 1.1 1 15 4.40
8022378 6932605 1.1572 4.59
7939163 7182796 1.1053 4.38
3 5105688 8798553 3 0.5803 2.24 2.06 0.1 7 0.689 0.057
03! 6212633 1 1551221 0.5378 2.07
UV 7108574 13740457 0.5173 1.99
3974543 6777215 0.5865 2.27
5974654 10849108 0.5507 2.12
4 5978974 12990972 3 0.4602 1 .75 1 .76 0.07 0.710 0.044
03! 5820559 12788305 0.4551 1 .73
H202 4056563 8031797 0.5051 1 .94
4164827 8251756 0.5047 1 .93
4827953 10288323 0.4693 1 .79

 

 

 

 

 

 

 

 

 

 

 

 

 

 

81

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

EXP. 9 l3l31
Effluent Fellll
Exp. Sample Measured with 10 cm cell Fe(II) conc. ( uM 1 k' Sk'
Number Absorbance Ave. Effluent Ave. 95% C.|. (min-1 1 (min-1 1
1 1 2.0349 2.0216 2.0247 2.0270 34.96 35.06 0.22 0.000 #DlV/Ol
2 2.0359 2.0349 2.0324 2.0344 35.09
3 2.0351 2.0383 2.0376 2.0370 35.13
2 1 0.5436 0.5432 0.5414 0.5427 9.27 9.36 0.77 0.292 0.026
03 2 0.5328 0.5331 0.5322 0.5327 9.10
3 0.5664 0.5677 0.5680 0.5674 9.70
3 1 0.4193 0.4203 0.421 1 0.4202 7.15 6.99 0.41 0.426 0.026
03IUV 2 0.4111 0.4123 0.4111 0.4115 7.00
3 0.3980 0.4010 0.4050 0.4013 6.82
4 1 0.5133 0.5146 0.5145 0.5142 8.78 8.87 0.32 0.315 0.012
03/H202 2 0.5155 0.5159 0.5161 0.5158 8.81
3 0.5279 0.5276 0.5285 0.5280 9.02
Calibration Curve : Y = -6.88 4» 969.27 X
r = 0.9998
"X" is the value of Absorbance
"Y" is the F601) concentration 1 ppb 1
"r' is the correlation coefficient
H202 Calllration Cave
Std. Measruements
uM test 1 test 2 test 3 test 4 test 5 Ave. 95% OJ.
0 0.067 0.066 0.067 0.066 0.064 0.066 0.0015
10 0.122 0.116 0.121 0.119 0.120 0.120 0.0029
25 0.194 0.195 0.204 0.198 0.199 0.198 0.0049
50 0.324 0.321 0.325 0.324 0.323 0.323 0.0019
75 0.451 0.450 0.460 0.453 0.454 0.454 0.0049
100 0.593 0.595 0.596 0.595 0.594 0.595 0.0014
Calibration Curve : Y = -12.47 + 190.77 X
r = 0.9998
where ; 'X" is the UV absorption at 551 nm
'Y" is the concentration of H202 in uM
"r" is the correlation coefficient
H202 Sample
Exp. lnfluent Effluent k' Sk'j
Abs. uM (raw1 M (initia Ave. 95% C.l. Abs. uM Ave. 95% 0.1. ( min.-1 ( min.-1 1
4 0.669 16725 66.58 66.64 0.07 0.251 35.41 36.59 1.09 0.087 0.004
0.670 16750 66.68 0.263 37.70
0.670 16750 66.68 0.257 36.55
0.669 16725 66.58 0.255 36.17
0.670 16750 66.68 0.260 37.13

 

 

 

 

 

 

 

 

 

 

 

 

 

82

EXP. 10 (1/31

1) pH = 6.29
21 [HCO3-1= 0.0046 mole/L
31 Punp flowrate : Ozone = 12.301 mL/min.
DCB = 12.340 mL/min.
NaOH = 1.153 mL/min.
Fe(lll = 0.984 mL/min.
H202 = 0.106 mL/min.

41 Hyfialllc Retention Tine 9.34 min ( w/o H202 1 9.30 min ( w/ H202 1

51 Volume of The Reactor = 250 mL

Ozone Concentration
INFLUENT
Raw Reactor

 

EFFLUENT
Final

 

Exp. Wt. 2 Initial Ozone Concentration ( uM 1 k' Sk'

 

 

Abs.

uM

(9)..

Abs.

Abs.

Data

ub-Ave

Ave.

5%C.l

min.-1

min.-1

 

1

0

0.00

#####

 

#####

 

#####

#####

 

#####

 

#####

 

#####

#####

 

#####

 

#####

 

#####

#####

#####

#####

#####

#####

 

03

0.154

117.90

206.19

232.75

1 .004

15.47

 

15.47

 

15.47

15.47

 

205.16

232.18

1 .004

16.02

 

16.02

 

15.82

15.95

 

202.54

230.06

1 .004

15.51

 

15.51

 

15.51

15.51

15.64

0.56

0.700

0.030

 

03/
UV

0.156

119.44

205.03

232.32

1.001

0.86

 

1 .05

 

1 .05

0.99

 

201.30

228 .08

1.001

1.50

 

1.50

 

1.50

1.50

 

204.26

231.21

1.001

1.28

 

1.28

 

1.28

1 .28

1 .26

0.64

1 0.082

 

03/
H202

 

0.157

 

1 19.73

205.53

232.50

1 .002

2.40

 

2.40

 

2.40

2.40

 

205.24

232.28

1 .002

2.31

 

2.31

 

2.31

2.31

 

 

205.14

 

232.72

 

1 .002

2.58

 

2.58

 

 

 

2.58

 

2.58

 

2.43

 

 

5.197

 

 

 

Note: '
00

weight of beaker only
weight of beaker + indigo blue

'” Ozone concentration in experiments 1 & 6 are zero.

 

 

83

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Effluent 068 concentration

where : X is the DCB/T CB ratio

Y is the DCB concentration ( ppb 1

EXP. 1 0 (2/31
008 Stand“ Calllration Cave
Std. 008 'T'ca Useful orr Ave. ‘
UM area area Sample
0.00 0 10994926 1 0.0000
0.68 2709133 15521120 3 0.1745 0.1703
2822517 16987612 0.1662
2745956 16142584 0.1701
1.70 6871543 16668120 3 0.4123 0.4096
6875499 16747235 0.4105
6690765 1 6485668 0.4059
3.40 13057246 15762961 3 0.8283 0.8130
13367006 16621329 0.8042
12637938 15671754 0.8064
5.10 19683484 16073414 3 1 .2246 1 .2240
1 8523668 1 5070709 1 .2291
19661632 16137345 1.2184
6.80 21615140 14528687 3 1.4878 1.4871
22855978 15308210 1.4931
2431 3048 1 6422267 1 .4805
13.61 51689228 15674178 3 3.2977 3.2538
51457456 15652338 3.2875
52288980 16463539 3.1760
Calibration Curv Y 0.03 + 4.22
r = 0.9989

 

 

 

 

 

Exp. oce i‘ca Useful an ace Ave. 95% k' Sk'
No. area area Sample U! 111 0.1. ( mh-1 1 95% CJ.
1 42656516 14153676 4 3.0138 12.75 1 3.94 2.05 0.000 #DIVIOl
18558520 5249862 3.5350 14.95
19319944 5392414 3.5828 15.15
33437948 10963676 3.0499 12.91
37823840 756961 49.9680 210.91
2 7123910 14034804 4 0.5076 2.18 4.34 0.83 0.237 0.071
03 8548897 7130518 1.1989 5.09
12037572 12035801 1 .0001 4.26
13621071 14772329 0.9221 3.93
13190443 13739242 0.9601 4.09
3 4790381 7464607 4 0.6417 2.74 2.69 0.16 0.449 0.086
03! 12867412 15317227 0.8401 3.58
UV 7449666 1 1821526 0.6302 2.69
6262754 10545058 0.5939 2.54
4713175 7264267 0.6488 2.77
4 3121084 6379119 5 0.4893 2.10 2.00 0.17 0.643 0.124
03/ 4522149 10953430 0.4129 1 .78
H202 3844538 8085955 0.4755 2.04
3919295 8608885 0.4553 1.96 .
3241634 6595005 0.4915 2.11

 

 

 

 

 

 

 

 

 

 

 

84

EXP. 1 0 l3/31

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Effluent Fell”
Exp. Sample Measured with 10 cm cell Fe(ll) conc. l ppb 1 k' Sk'
Number Absorbance Ave. Effluent Ave. 95% C.l. (min-1 1 (min-1 1
1 1 1.9287 1.9218 1.9204 1.9236 33.17 33.19 0.06 0.000 #DIVIOl
2 1.9253 1.9243 1.9290 1.9262 33.22
3 1.9233 1.9272 1.9209 1.9238 33.17
2 1 0.4352 0.4336 0.4322 0.4337 7.38 7.48 0.40 0.368 0.021
03 2 0.4514 0.4498 0.4495 0.4502 7.67
3 0.4350 0.4342 0.4336 0.4342 7.39
3 1 0.3789 0.3788 0.3788 0.3788 6.43 6.42 0.05 0.447 0.004
O3/UV 2 0.3770 0.3765 0.3763 0.3766 6.40
3 0.3764 0.3797 0.3796 0.3786 6.43
4 1 0.4509 0.4520 0.4527 0.4518 7.70 7.80 0.34 0.350 0.016
03/H202 2 0.4681 0.4663 0.4649 0.4665 7.95
3 0.4541 0.4546 0.4544 0.4544 7.74
Calibration Curve : Y = -6.88 + 969.27 X
r = 0.9998
"X" is the value of Absorbance
”Y" is the Fe(lll concentration ( ppb 1
"r' is the correlation coefficient
H202 CaIHIration CII'V.
Std. Measruements
UM test 1 test 2 test 3 test 4 test 5 Ave. 95% CJ.
0 0.064 0.069 0.063 0.066 0.063 0.065 0.0032
10 0.104 0.102 0.099 0.095 0.099 0.100 0.0043
25 0.177 0.178 0.177 0.173 0.177 0.176 0.0024
50 0.313 0.312 0.318 0.315 0.313 0.314 0.0030
75 0.451 0.447 0.448 0.459 0.448 0.451 0.0061
100 0.587 0.583 0.588 0.585 0.582 0.585 0.0032
Calibration Curve : Y = -9.85 + 188.69 X
r = 0.9993
where ; "X" is the UV absorption at 551 nm
"Y" is the concentration of H202 in uM
'r" is the correlation coefficient
H202 Sample
Exp. lnfluent Effluent k' Skfi
Abs. uM (raw1 M (initial Average 95% C.|. Abs. UM Average 95% 0.1. ( min.-1 ( min.-1 1
4 0.643 16075 63.38 63.42 0.07 0.260 39.21 38.04 0.90 0.072 0.003
0.644 16100 63.48 0.255 38.27
0.643 16075 63.38 0.251 37.52
0.643 16075 63.38 0.251 37.52
0.644 16100 63.48 0.252 37.70