Catalysis Assignment: The effect of support on redox properties and methanoloxidation activity of vanadia catalysts

Basic Principle of Coulometric Titration Technique

Coulometric titration technique is a technique that provides a more quantitative measure

of oxygen binding in metal oxide catalyse. To be more specific, it is based on
measurement of chemical potential of oxygen in a gaseous phase which able to indicates
the composition of the oxides.
In this technique, a sample is placed in a sealed container, which is an
experimental apparatus used, that is equipped with one or two electrochemical element
for oxygen sensing and pumping. In addition, the example of the electrochemical element
which is commonly used is Yttria-Stabilized Zirconia (YSZ) tube. YSZ tube is painted
with Ag electrodes on the inner and outer surfaces.
To analyse the sample, a ceramic crucible is filled with the sample and inserted
into the center of the YSZ tube. Then, the sample size which contains of approximately
100 mol vanadium is used. With The Cajon fittings attached to the end of YSZ tube, the
tube and catalyst sample is allowed to be heated by placing the center portion of the tube
in a tube furnace. In order to insure that the sample can fully oxidized, a mixture of 2.5%
O2, 50% CO2 and 50% Ar is allowed to flow over the sample for 1 hour at the
temperature of 748 K (510.85 oC).
Then, the Cajon fitting is plugged and allow the sample to equilibrate with the gas
phase until the potential across the Ag electrodes become constant. The duration for this
usually took in between one to five days. The constant potential is then used to calculate
the oxygen partial pressure inside the cell by using the Nernst equation.
Next, a controlled amount of oxygen is removed or added by using a Gamry
Instruments potentiostat to pass a certain amount of charge across the Ag electrodes.
Gamry instrument is the company that created instruments with uncommon value and

performance and one of it is potentiostat that is used in this experiment (Gamry.com,

2015). This instrument is shown in Figure 1.

Figure 1:

Gamry Instruments Potentiostat

According to Gamry.com (2015), a potentiostat is an electronic instrument that

used to control the potential difference between a reference electrode and a working
electrode where both of the electrodes contained in an electrochemical cell. The control
of the potential difference is done by injecting current into the cell through an electrode
and measures the current flow between both of the electrodes as well. Thus, a potentiostat
control the cell potential whereby the cell current is varied.
Next, in this experiment, most of the oxygen is removed with the conversion of
CO2 to CO. The removal of oxygen is then caused the reduction of the sample. And since
the amount of oxygen added or removed from cell is measured by using the Gamry
Instruments potentiostat as well as the starting composition of the sample is known, the
sample composition as a function of the oxygen partial pressure, P(O 2) can be calculated
by using the mole balance.

Reference
Gamry.com, (2015). Potentiostat-Instrument Between Working Electrode/Reference
Electrode. [online] Available at: http://www.gamry.com/applicationnotes/instrumentation/potentiostat-fundamentals/ [Accessed 1 Aug. 2015].