Experimental Study of Diffusion of Carbon Dioxide,

Methanol and Formic acid through PTFE Membrane.

Salman Zafar

Content
Objectives
Literature Survey
Experimental Setup

Results and Comparisons

Summary

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Objectives

Better understanding of the transport of selected species

through the PTFE membrane using DEMS

Studying the Effect of change in Pore size of the membrane

Studying the Effect of movement of solution in the cell

Studying the Effect of temperature change

Studying the Effect of presence of Catalyst

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Content
Objectives
Literature Survey
Experimental Setup

Results and Comparisons

Summary

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Literature Survey
Ashton, S., J. (2011)
The Design, Construction and Research Application of a
Differential Electrochemical Mass Spectrometer (DEMS),
PhD Dissertation TU Munich.
The work deals with the design, construction and characterization of DEMS
which has emerged as an important tool for the analysis of the half-cell
studies in the fuel cells and other electro-chemical areas of application. The
study uses the DEMS to elucidate the chemical reactions that occur while
the oxidation of methanol on carbon based Pt-Ru catalyst. And the
corrosion of the high surface area carbon based catalysts. The study
presents a detailed discussion about the various operational features of
DEMS
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Literature Survey
Lindermeir, A., Rosenthal, G., Kunz, U. (2004)
On the question of MEA preparation for DMFCs. J. Power
Sourc., Vol. 129(2), pp. 180-187
The study presents two methods of preparation of the membrane electrode
assembly. In the first method the preparation started with the carbon
backing, then the substrate along with some PTFE is added to it, followed
by spraying of the catalyst mixture. This is then combined with the
membrane to give the MEA. In the second method the catalyst mix is
applied directly to the membrane. The assemblies from the second method
were found to be better due to a greater availability of active sites of the
catalyst.
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Literature Survey
Cappiello, A., Famiglini, G., Palma, P. (2003)
Peer reviewed: electron ionization for LC/MS. Anal. Chem.,
Vol. 75, pp. 496A503A
The study highlights the use of Teflon membranes in DEMS studies. The
Teflon membrane being hydrophobic in nature is able the separate out the
aqueous medium from going into vacuum, resulting in the ionic species
being the majority of what goes into the DEMS. The output data from the
DEMS may be converted to quantitative data by calibrating the ion current
to actual mass or actual quantity of a specific ion or species.

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Literature Survey
Sundmacher K. (1999)
Cyclone flow cell for the investigation of gas-diffusion
electrodes, App. Eletroche., Vol. 3 (29), pp. 919-926
The study throws light on a new design for the electrochemical half cell
studies that is well suited for the Gas diffusion Electrodes. The design
earlier used for the study of surface electrochemical reactions was the
rotating disc electrode, but this is not suited well with GDEs. The cylcone
flow cell suggested by Sundmacher, makes use of cyclone vortex flow over
a stationary electrode surface that is diffusive in nature to the gas phase.

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Literature Survey
Wang, H., Rus, E., Abruna, H.D. (2010)
Letters to Analytical Chemistry New Double-BandElectrode Channel Flow Differential Electrochemical Mass
Spectrometry Cell: Application for Detecting Product
Formation during Methanol Electro-oxidation. Anal. Chem.,
Vol. 82, pp. 43194324
The study shows the behaviour of mass spectrometer ion current with change in flow
rate of the solution over the electrode surface. The mass current is plotted as a
function of the flow rate for carbon dioxide, methanol and other species. The trends
given in this study were observed to be similar to one found in experiments.

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Content
Objectives
Literature Survey
Experimental Setup

Results and Comparisons

Summary

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System Description

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Apparatus
Cyclone Flow Cell
Membrane
PTFE Membranes
0.2m and 0.45m
Mass Spectrometer
Vacuum Pumps
Vacuum Pump 1 80 l.s-1
Vacuum Pump 2 200 l.s-1
Solution Pump
Peristaltic Pump
Operation Range- 24RPM(27.3 ml/min) to 600RPM(579ml/min)

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Experiments
Carbon Dioxide
1.
2.
3.

De-ionized water bubbled with Nitrogen for 15min

Then bubbled with CO2 for 30min
Cell and connections set up, vacuum pumps started (with vacuum valve
closed).
4. Solution bottle bubbled and stirred continuously
5. Cell filled with solution
6. Vacuum valve is opened to evacuate the space between membrane and the
valve, valve closed again.
7. Pump is started and cell fills with fresh solution
8. Pump is closed, and the valve is opened (1min Delay)
9. Record the diffusion curve and close the valve
10. Repeat from step 7 again
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CO2 Diffusion Measurement

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Experiments
Methanol and Formic Acid
1.
2.
3.
4.
5.
6.
7.
8.
9.

De-ionized water bubbled with Nitrogen for 15min

0.5M Solution Made
Cell and connections set up, vacuum pumps started (with vacuum valve
closed).
Cell filled with solution
Vacuum valve is opened to evacuate the space between membrane and the
valve, valve closed again.
Pump is started and cell fills with fresh solution
Pump is closed, and the valve is opened (1min Delay)
Record the diffusion curve and close the valve
Repeat from step 6 again
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Content
Objectives
Literature Survey
Experimental Setup

Results and Comparisons

Summary

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Results
Carbon Dioxide Diffusion Through 0.2m Membrane

Almost similar transport no significant effect of catalyst presence.

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Results
Carbon Dioxide Diffusion Through 0.45m Membrane

Presence of catalyst slows down the transport

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Results
Carbon Dioxide Diffusion Membrane Comparison

Transport through 0.2m membrane is slower

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Results
Carbon Dioxide Diffusion at different temperatures

No significant effect on the diffusion curve

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Results
Carbon Dioxide Diffusion with varying degree of solution convection

No significant effect on the diffusion curve

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Results
Methanol Diffusion Through 0.2m Membrane

Presence of catalyst slows down the transport

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Results
Methanol Diffusion Through 0.45m Membrane

Presence of catalyst slows down the transport

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Results
Methanol Membrane Comparison

Greater and faster diffusion for bigger pore size

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Results
Methanol Effect of convection on Mass signal

The shape of the Diffusion Curve remains the same

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Results
Formic Acid Diffusion Through 0.2m Membrane

Presence of catalyst slows down the transport significantly

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Results
Formic Acid Diffusion Through 0.45m Membrane

Presence of catalyst slows down the transport significantly

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Results
Formic Acid Membrane Comparison

Greater and faster diffusion for bigger pore size

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Results
Formic Acid Membrane Comparison

Greater and faster diffusion for bigger pore size

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Results
Formic Acid Membrane Comparison

Greater and faster diffusion for bigger pore size

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Results Conformation with Earlier Study

New Double-Band-Electrode
Channel Flow Differential
Electrochemical Mass
Spectrometry Cell: Application for
Detecting Product Formation
during Methanol Electro-oxidation
Wang, H., Rus, E., Abruna, H.,D.
(Analytical Chemistry, Vol. 82, No.
11, June 1, 2010)

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Results Conformation with Earlier Study

Carbon Dioxide - Hydrodynamic Behaviour of MS signal

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Results Conformation with Earlier Study

Methanol - Hydrodynamic Behaviour of MS signal

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Results Conformation with Earlier Study

Formic Acid - Hydrodynamic Behaviour of MS signal

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Content
Objectives
Literature Survey
Experimental Setup

Results and Comparisons

Summary and Further Developments

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Summary
The flux for non polar species (CO2) is higher compared to polar species
(Methanol and formic acid).
The flux and rate of diffusion for 0.45m membrane is greater than 0.2 m
membrane.
The presence a catalyst has a little effect on transport for 0.2 m membrane
in case of CO2 as compared to methanol and formic acid .
The speed of pump has no significant effect on the diffusion curve for all the
species.
The temperature dependence is not profound over range of 10 C
Hydrodynamic behaviour of the species in the system was in conformation
with an earlier study.

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Further Developments
The data of the MS may be used
quantitatively and be compared
with a model if the system is
calibrated for the three species
giving a calibration constant that
would relate the mass currents to
actual mass flow rates.
The diffusion curve can be
studied in an exact manner when
the dead space between the
membrane and the vacuum pump
can be removed some how.
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References
Sundmacher K. (1999)
Cyclone flow cell for the investigation of gas-diffusion electrodes, App.
Eletroche., Vol. 3 (29), pp. 919-926
Lindermeir, A., Rosenthal, G., Kunz, U. (2004)
On the question of MEA preparation for DMFCs. J. Power Sourc., Vol.
129(2), pp. 180-187
Cappiello, A., Famiglini, G., Palma, P. (2003)
Peer reviewed: electron ionization for LC/MS. Anal. Chem., Vol. 75, pp.
496A503A

Ashton, S., J. (2011)

The Design, Construction and Research Application of a Differential
Electrochemical Mass Spectrometer (DEMS), PhD Dissertation TU
Munich.
Indian Institute of Technology Roorkee -- 38

References
Wang, H., Abrua, H.D. (2011)
Electrocatalysis of direct alcohol fuel cells: quantitative DEMS studies.
Struct. Bond., Vol. 141, pp. 3383
Planes, G.A., Garca, G., Pastor, E. (2007)
High performance mesoporous Pt electrode for methanol
electrooxidation. A DEMS study. Electrochem. Commun. Vol. 9, pp. 839
844
Wolter, O., Heitbaum, J. (1984)
Differential Electrochemical Mass Spectroscopy (DEMS) a New
Method for the Study of Electrode Processes. Ber. Bunsenges. Phys.
Chem., Vol. 88, pp. 2 6

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References
Munk, J., Christensen, P.A., Hamnett, A., Skou, E. (1996)
The electrochemical oxidation of methanol on platinum and platinum +
ruthenium particulate electrodes studied by in-situ FTIR spectroscopy
and electrochemical mass spectrometry. J. Electroanal. Chem., Vol. 401,
pp. 215-222
Wang, H., Rus, E., Abruna, H.D. (2010)
Letters to Analytical Chemistry New Double-Band-Electrode Channel
Flow Differential Electrochemical Mass Spectrometry Cell: Application
for Detecting Product Formation during Methanol Electro-oxidation. Anal.
Chem., Vol. 82, pp. 43194324

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Thank You!
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Extra - Apparatus

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Extra
Dimensions of the Cell (mm)

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Extra
The Methanol Run curve

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Extra - Run Comparisons

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Extra - Catalyst Coating

The nanoparticles are mixed with distilled water and
isopropanol and then with nafion solution which acts as a
binder.
The mixture is then sonicated and it ensures evenly
dispersed particles.
The suspension is then directly sprayed on the PTFE
membrane.
The catalyst loading is then directly calculated by the
difference in the weights of the naked membrane and the
coated membrane.

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MATLAB Model for Carbon Dioxide

Assumptions
Diffusion is purely Diffusive in nature.
Concentration gradient across the
membrane is linear

Tortuosity of the membrane is 1

Initially the concentration of CO2 is
uniform (At saturation)
The Diffusion is one dimensional
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MATLAB Model
Development of the Model
Mass Balance Equation (Unsteady State)

Finite Difference method was used to define the derivates, and equation were written for 1st, i th and last
element and the membrane and solved simultaneously
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MATLAB Results

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