DETERMINATION OF TOTAL ORGANIC CARBON

THROUGH OXIDATION BY FOTOKATALITIK-

KONDUKTOMERI

Abstract

Total organic carbon (KOT) content is considered as one of important parameter in water quality.
This researchdeveloped a method to determine of TOC, in which the organic content was
oxidized by photocatalytic oxidation and produced carbon dioxide measured by mean
conductometry technique. The Oxidation Unit employing in the proposed method was a glass
column reactor, in which the TiO2 film was on to its inner wall, and the uv "black light" as a
photon source. P reliminary result on the mehod performance test ndicate that in the range
between 10 to 100 ppm a good linearity was achieved and had a good agreement compared to
that of measured by a commercial TOC meter with similar method but employing TiO2 in a
slunry system (ANATOC). By employing immobilized TiO2 thin film a problem on column
reactor stacking, as did in slurry system, could be eliminated and no necessary to add catalyst
suspension in each analysis.

1. Introduction

KOT is one important parameter as the criterion of water for different designation, such
as drinking water, water needs and / or industrial waste. Generaonlly agreed that the value of
KOT used as general indicators of water contamination by volatile organic substances and
nonvolatile1, 2. In this context, it is necessary that the method is simple, fast and inexpensive way
to determine KOT in water at various designation (ranging from industrial wastewater with a
high-KOT to the ultra pure water with very low content of KOT) without losing sensitivitanya.

In general, KOT determination involves two main stages, ie the conversion of organic
matter into CO2 and H2O and CO2 yielded quantitative determination. Conversion oganik
substances into CO2 and H2O can be done in several ways, namely chemical oxidation, 3.4 therma
combustion,l5, 6 pyrolysis,7 fotodekomposisi,8.9 and fotokatalik Oxidation.10 Oxidation by
chemical oxidation is limited to non-organic substances volatile, thermal combustion requires
great energy to achieve high temperatures in the combustion chamber, the pyrolysis can only
accommodate small sample size and sensitivity is difficult to increase when dealing with samples
with very low KOT, photooxidation require high-energy UV light (UV-C) to obtain complete
oxidation. Photocatalytic oxidation mode chosen in this study has the advantage of being able to
work at room temperature, using a source of low-energy photons (UV-A). Energy photons with
<410 nm is required to activate the TiO2 catalyst to produce strong oxidizing species that will
memineralisasi organic substances produce CO2. The system was developed to handle samples
with small volume, and can accommodate both volatile compounds and non-volatile.

Carbon dioxide is produced, in general, can be measured by nondispersive infrared

(NDIR) absorption spectrometry,11.12 thermal conductivity13 or determined by titration
volumetri14, 15 gravimetry,16 and various methods of ion chromatography,17- 22 after its CO2
absorbed into the acid or alkaline solution. NDIR, thermal conductivity, and ion chromatography
analysis tools require a fairly expensive. Titimetri and gravimetric can not provide adequate
sensitivity when dealing with samples were very low KOT. In this study the determination of the
CO2 is done by konduktometri23 a simple and inexpensive yet sensitive enough, after the CO2 was
collected directly into the mineral-free pure water.

2. Experiment
2.1. Immobilization of TiO2 thin film on the inner wall of the glass column.

Coating TiO2 by sol-gel method using 0.5 M precursor titanium (IV) bis acetyl
diisopropoksi asetonat (TAA, Aldrich) in ethanol and propanol ekivolum. Inner walls of the
column that has been cleaned with mineral acids, demineralized water and organic solvent and
then dried. Into a glass column (pyrex and / or quartz) which has net inserted precursor solution
and let stand a few moments. Precursor solution was then removed and the walls of the column is
dried gradually from room temperature up to 1200o C. Into the column and then dilairkan air
and / or pure oxygen while heated to a temperature reaches 400o C and held until the black layer
and / or gray all turned white and transparent. Coating was repeated up to five times.

2.2. Characterization of TiO2 thin film on the inner walls of the column.

The presence of a thin film on the inner wall of the column was characterized using UV-
Vis spectrometry (according gapnya energy), SEM-Scanning Electron Microscope-(profile / thin
film surface topography and thickness), and XRD-X-ray Difractometer (identity existence of
rutile crystal form and / or anatase). Examination of UV-Vis spectrum is done by cutting some of
the column and split it into two pieces, then place them on the street light in watertight
compartments and the use of comparison samples of air and / or columns that are not covered.
SEM examination performed with specimens that are similar to those used in the examination of
UV-Vis. While the examination conducted on the powder XRD exfoliated from the TiO2 film.

2.3. Performance testing reactor

2.3.1. Reactor configuration

Reactor configuration consists of two coils

column inner wall of glass that is coated TiO2
connected in series. Each reactor coil wrapped around
the black light and UV lamp each power 8 watts.
Bersistem loop reactor using sirkulator periltastik
pump and reservoir buffer capability as a gas
separator. Carbon dioxide is separator from the gas
liquid separator dilairkan into the reservoir also
functions as a cell which is controlled by a digital
conductivity conductometer.
2.3.2. Performance testing reactor

Before use dikonditioning reactor system with 20 ml of mineral water and run the system
until the signal konduktometri stable. Then injected into the reactor as much as 5 ml sample
solution containing certain KOT (for standard / calibration curve) and / or samples to be
determined KOTnya content. This study used two types of chemical compounds, namely glucose
and / or acid bensoat, as a reference / comparator KOT content with concentrations ranging from
0 to 60 ppm. Previously conducted preliminary experiments to determine the time required to
complete oxidized organic substances used in the concentration area.

3. Results and Discussion

3.1. The conceptual approach of oxidation catalysis at the surface of TiO2 thin film and
measurement of carbon dioxide it produces.

TiO2 thin film on transparent glass can be activated by UV light illumination from the
direction of supporting materials and produce pairs of electrons (the conduction band) and hole
(in valence band) on the other hand is in contact with the solution. The interaction between the
holes with water to produce hydroxyl radical, a powerful oxidizing species, which will oxidize
organic compounds to produce around water, mineral acids and carbon dioxide (see figure 2 and
3).

Carbon dioxide produced in the reaction will be moved into the fluid reservoir (ion-free
pure water) and measured konduktifitasnya. Value proportional to the conductivity cell constant,
the concentration of carbonate ion and / or bicarbonate ions which is equivalent to the
concentration of carbon dioxide dissolved in the liquid catcher, and nota bene is equivalent to the
content of organic substances in the sample. Empirical equation obtained is:

Czat organik = Ksel x [(kf)2 (ki)2] (6)

Czat organic : the concentration of organic matter which is equivalent to the results of
Ksel : oxidation and CO2 gas dissolved in the liquid reservoir in the
kf : conductivity cell
 ki : cell constants and / or calibration coefficient (ppm/uSiemen2) final
conductivity after complete oxidation (uSiemen)
initial conductivity before the oxidation reaction (uSiemen)

3.2. Character thin layer of TiO2 on the wall in a glass column.

TiO2 thin buffer layer on glass prepared by sol-gel has a local absorption of UV in the
range of 320 s / d 405 nm, with a peak of 365 nm (Fig. 4.). Data processing with the early
emergence of reference absorbance at 405 nm provide predictions of energy gaps of
approximately 3.2 eV. Increasing the amount of coating to give consequence to the thickening of
a thin layer which is reflected in the increase of the value of absorption according to Beer-
Lambert rule. The amount of thin film thickness predicted from the container transverse SEM
images of TiO2 films on glass buffer (Figure 5). Meanwhile, XRD examination showed that the
crystal structure formed is dominated by the anatase form which is characterized by the intensity
of diffraction at 2 between 25 to 25.5; 37.00 s / d 37.10, and 48.15 s / d 48.2 (XRD diagrams
not shown).

3.3. Measuring System Performance Test Kot

Glass column reactor with TiO2-coated surface of the walls in the measuring system
assembled into KOT as in Figure 1. The system is fed into a solution of organic substances
(glucose, as a model) with some level of concentration. Evolution of conductivity in the reservoir
solution indicates the amount of carbon dioxide gas is formed. Conductivity value will no longer
remain after the formation of carbon dioxide (all organic matter has been oxidized). The time
needed to complete oxidation depends on the amount of organic substances in the reactor, to
contain up to 60 ppm KOT it took less than 15 minutes (Figure 7). Test of linear relationship
between KOT with value (kf2 - ki2) is done by using the value of kf after konduktifitasnya
constant (> 15 minutes). It appears that in the concentration range between 5 to 60 ppm obtained
a fairly good degree of linear (Figure 8).
 In this way some artificial samples containing the same concentration of organic
substances measured KOTnya value and results compared with measurement of the same sample
but using methods / instrumentation ANATOC (commercial instrument measuring the TOC or
KOT-based photocatalytic oxidation with TiO2 suspension and measurement konduktometri).
The results shown in Table 1 below:

Table 1. The measurement results of sample with Instrumentation developed and

ANATOC
[record made Kot theoretical value is 17.001 ppm]

No. Sample results of measurement (ppm)

The proposed instrumentation ANATOC
1 17,979 17,370
2 17,023 15,030
3 16,550 15,328
4 16,550 15,228
average 17,026 15,989
Difference measurement 0,673 1,083
range

From the table it can be seen that the results of measurements with the technique and
instrumentation that was developed has a smaller range of measurements and a smaller
difference to the theoretical value. A difference may indicate that the oxidation process in
measurement by oxidation ANATOC rudimentary guide operations over the given time line
procedure is very short. Although still to be done further tests regarding the working area of
concentration range (linearity), precision and accuracy, the influence of types of organic
substances and the sample matrix, but it can be said that in principle the proposed system has the
potential to be developed as TOC or KOT meter memenruhi simple criteria (injek sample and see
the results), without input inexpensive catalyst / chemicals each time analysis (Nearly
chemicalless) and therefore environmentally friendly.

4. Conclusion

From this research can be concluded that the glass column reactor with TiO2-coated
surface of the inner wall can function as an oxidising unit at KOT meter instrumentation.
KOTmeter instrumentation developed, where the value of konduktan KOT derivatized carbon
dioxide reservoir cells results photocatalytic oxidation reactor perfect, able to provide adequate
measurement results as similar systems are already available commercially, but using the catalyst
suspension.

5. Acknowledgements

Osaka Gas Foundation International Cultural Exchange (OGFICE) of part suportnya in

the development of glass-walled reactor column in the active photocatalyst.

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