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PSEUDO-ZERO- ORDER KINETICS: DIFFUSION THROUGH A POLYMER MEMBRANE USING A SATURATED SOLUTION RESERVOIR SYSTEM Jan-alfred Aquino | Christopher Chen | Yanglu Chen | Zachariah DeGiulio | Katherine Dong | Christina Floristean | Michelle Guo| Alexandra Kapadia | Robert Kolchmeyer | Erik Massenzio | Adam Richardson | Jessica Xu Dr. David Cincotta | Alberto Rivera
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Page 1: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

PSEUDO-ZERO-ORDER KINETICS:

DIFFUSION THROUGH A POLYMER MEMBRANE USING A SATURATED

SOLUTION RESERVOIR SYSTEM

Jan-alfred Aquino | Christopher Chen | Yanglu Chen | Zachariah DeGiulio | Katherine Dong | Christina Floristean | Michelle Guo| Alexandra Kapadia | Robert Kolchmeyer | Erik Massenzio | Adam Richardson | Jessica Xu

Dr. David Cincotta | Alberto Rivera

Page 2: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Controlled Release

• Zero-order kinetics

• Rate independent of concentration

• Does not often occur in nature

• Applications:o Medicineo Agricultureo Cosmetics

Page 3: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Pseudo-Zero-Order Kinetics

Fick's Law:

A pseudo-zero-order system would achieve a constant rate of release, but would not be independent of concentration.

This can be done by holding the concentration gradient constant.

Page 4: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Hypothesis

• IF: An apparatus is made that allows for diffusion of a saturated solution into a body of water across a membrane

•THEN: Pseudo-zero-order diffusion should be observed

•Maintain a constant concentration gradient

Page 5: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Polymer Membrane

• Repeating structural units of monomers

• Amorphous structures more easily allow diffusion than crystalline structures

• Ethylene-vinyl acetate o 10% EVA o 12% EVA

Page 6: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Choosing Citric Acid

• Solid at room temperature

• Chosen over maleic acid and sodium chloride

• Conductivity & pH probe • Continuously measured

over longer periods of time

• Most consistent results

Citric acid

Maleic acid

Page 7: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Experimental Design: Saturated Solution Reservoir System

• Saturated solution of citric acid added to petri dishes • Solute passes through the membrane• Additional solid citric acid added to continuously re-

saturate the solution• Pseudo-zero-order

Polymer Membrane

Saturated Solution

Solid Citric Acid

Petri Dish

Water Basin

Page 8: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Final Setup

Page 9: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Experimental Design

Design Features:

• Water-tight petri dishes

• Petri dish supports

• Maximize water and solution contact with the membrane

• Surface area optimization

• Uniform water level with respect to the petri dish

Page 10: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Results - The Diffusion of Citric Acid across a 10% EVA Membrane

Page 11: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Results – The Diffusion of Citric Acid Across 10% and 12% EVA Membranes

• With additional solute

• 10% EVA (top graph)

• 12% EVA (bottom graph)

• Suspected pH meter issue resulting in a few nonlinear curves

10% EVA Trials

12% EVA Trials

Page 12: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Results – The Diffusion of Citric Acid Solution Across 12% EVA 

• 12% EVA with 2g solid• Trials with 2g extra solid are zero order

Page 13: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Discussion

• Rate was faster in first few hours

• Tested with 10% EVA and 12% EVA

• Polarity accounts for permeation

• Reproducible rates remain elusive

Page 14: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Conclusion

• Achieved pseudo-zero-order kinetics with reservoir system

• Polar likes polar: Citric acid diffused through 12% EVA more effectively than 10% EVA

• Novel method for modeling a controlled-release system

• Data was supportive of hypothesis

• More needs to be done to conclusively accept or refute the hypothesis

Page 15: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

Future Studies

• Explore alternate methods of measuring diffusion

• Solute embedded in polymer• Biodegradable polymers• Solute with lower solubility • Mathematical models based

on parameters of polymer membrane and solute

• Generalized curve fits

Page 16: P SEUDO -Z ERO - O RDER K INETICS : D IFFUSION THROUGH A P OLYMER M EMBRANE U SING A S ATURATED S OLUTION R ESERVOIR S YSTEM Jan-alfred Aquino | Christopher.

References

1. Prisciandaro M. and Pepe F. Absorption with zero and Pseudo-Zero order chemical reaction. The Canadian Journal of Chemical Engineering; (2006) [Internet] [accessed July 29, 2011] 362 – 368p..

Available from : http://onlinelibrary.wiley.com/doi/10.1002/cjce.5450750212/abstract2. Nic M., Jirat J., Kosata B. Compendium of Chemical Terminology. IUPAC Goldbook; (2006).[Internet] [ accessed July 27, 2012]Available from : http://goldbook.iupac.org/P04937.html3. Blackmond DG., Hodnett NS., Lloyd-Jones GC., Mechanistic Implications of Pseudo Zero Order Kinetics in Kinetic Resolutions.

JACS Communications; (2006). [Internet] [accessed July 29, 2011] 7450 - 7451p.Available from : http://pubs.acs.org/doi/pdfplus/10.1021/ja062173f4. Jones D. FASTtrack: Pharmaceutics: Dosage Form and Design. London:Pharmaceutical Press; (2008). [Internet] [accessed 2012] Available from :http://www.pharmpress.com/files/docs/FT_Pharmaceutics_Drug_Delivery_sample.pdf5. Basic Property of EVA Resin. SNE Research; (2006) [Internet] [accessed July 26, 2012] Available from :

http://www.sneresearch.com/eng/info/show.php?c_id=4938&pg=6&s_sort=&sub_cat=&s_type=&s_word=6. Ionization Constants of Heteroatom Organic Acids. Michigan State University. [Internet] [accessed July 26, 2012] Available

from : http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/acidity2.htm7. Material Safety Data Sheet - Citric Acid. Science Lab. [Internet] [accessed July 24, 2012] Available from :

http://www.sciencelab.com/msds.php?msdsId=99234958. Periodontics: Controlled release delivery system. British Dental Journal; (2003). [Internet] [accessed July 30, 2012] 195 -

224p. Available from : http://www.nature.com/bdj/journal/v195/n4/full/4810497a.html9. Controlled release of triprolidine using ethylene-vinyl acetate membrane and matrix systems. European Journal

Pharmaceutics and Biopharmaceutics. (2002) [Internet] [accessed 2012] 201 - 206p. Available from : http://www.sciencedirect.com.ezproxy.drew.edu/science/article/pii/S0939641102000516

10. Gupta C., Chauhan A.Drug transport in HEMA conjuctival inserts containing precipitated drug particles.Journal of Colloid and Interface Science ; (2010). [Internet] [accessed July 30, 2012] 31 - 42p.

Available from : http://www.sciencedirect.com.ezproxy.drew.edu/science/article/pii/S002197971000326711. Drabczyk K., Panek Piotr. A Comparative Study of EVA with and without thermal history for different lamination process

parameters. Material Sciences and Engineering: B; (2011). [Internet] [accessed July 29, 2012] Available from : http://www.sciencedirect.com/science/article/pii/S092151071200254112. Krishnan KA., Sreejalekshmi KG., Varghese S. Adsorptive Retention of Citric Acid Onto Activated Carbon Prepared From

Havea Braziliansis Sawdust: Kinetic and Isotherm Overview. Desalination; (2010). [Internet] [accessed July 30, 2012] 46 - 52p.

Available from : http://www.sciencedirect.com/science/article/pii/S001191641000144X

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Acknowledgements

Dr. David Cincotta, Advisor

Alberto Rivera, Assistant

Dr. David Miyamoto, Director

New Jersey Governor's School in the Sciences and its Sponsors


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