Three case studies from scientific literature that illustrate how real-time in situ mid-FTIR (ReactIR) is used to advance the understanding of chemical reactions. Email me at paul.scholl@mt.com if you are interested in links to technical webinars and whitepapers on the topics of mid-FTIR in situ reaction analysis, process characterization & scale-up and reaction calorimetry.

1. Recent Advances in Organic Chemistry by
Academia Using Real-Time In Situ FTIR -
Part V
Presenter: Paul Scholl
Senior Technical Manager:
Reaction Analysis

2. Forewords
 Previous “recent advances in academia” webinars
- “Review of Recent Advances in Organic Chemistry Using Real-Time In Situ FTIR
– Part I”, Jennifer Andrews, April 2009
- “Recent Advances in Organic Chemistry by Academia Using Real-Time In Situ
FTIR – Part II”, Paul Scholl, June 2009
- “Recent Advances in Organic Chemistry in Academia Using Real-Time In Situ
FTIR – Part III”, Paul Scholl, October 2009
- “Recent Advances in Organic Chemistry in Academia Using Real-Time In Situ
FTIR – Part IV”, Dominique Hebrault, March 2010

3. Forewords
 Past ReactIR™ technology webinars
- “Application of Quantitative Analysis to Predict Absolute Concentration Information
in Real-time”, Jon Goode, 2009
- “Extracting Critical Information from Challenging Reaction Data Sets”, Paul Scholl,
2009
- “Best Practices for the Characterization of Organic Reactions Using Real-time In
Situ FTIR”, Jennifer Andrews, 2009
- “Introduction to Reaction Analysis Using Real-time In Situ FTIR”, Will Kowalchyk,
2009
- “Innovations in Reaction Analysis”, Paul Scholl, 2007

4. 3
Selected Publications for Part V
 Online Monitoring of Biotransformations in High Viscous Multiphase
Systems by Means of FT-IR and Chemometrics
 Tuning the Selectivity of the Oxetane and CO2 Coupling Process
Catalyzed by (Salen)CrCl/n-Bu4NX: Cyclic Carbonate Formation vs
Aliphatic Polycarbonate Production
 Equimolar CO2 Absorption by Anion-Functionalized Ionic Liquids

5. 4
Introduction
 Online Monitoring of Biotransformations in High Viscous Multiphase
Systems by Means of FT-IR and Chemometrics
Andreas Liese et al; Institute of Technical Biocatalysis, Hamburg
University of Technology, Germany
Mettler-Toledo AutoChem, Inc., Columbia, MD, USA
Evonik Goldschmidt GmbH, Essen, Germany
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

6. Quantitative Prediction in Problematic Matrix
5
 Unstable
emulsion system
 Quantitative
analysis difficult
 Four dispersed
phases
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

7. Solvent Free Esterifications using Biocatalyst
 “Green Chemistry”
- No solvents
- Reduced energy demands
- Real-time analysis
 Prevents waste
 Solvent free esterification
yielding myristyl myristate
 Solvent free esterification
yielding polyglycerol-3-
laurate
6
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

8. Correlate Off-line Data to Reaction Progress
7
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

9. Quantitative Diagnostics Indicate Good Fit
8
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

10. Conversion Predicted in Real-time
9
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

11. Acid Value Predicted in Real-time
10
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

12. Online FTIR Predicts Where Off-line Fails
11
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

13. Conclusions
 Real-time FTIR gives reliable quantitative information for the
esterifications of fatty esters in highly viscous solvent free systems
 Solid particles and gas bubbles did not have any significant influence
on the spectral data
 Online analysis of biotransformations in emulsion systems of up to four
phases is possible
 Unstable two phase systems can be predicted where they could not
have been in the past
 Additional advantage include:
- No volume loss by sampling
- No catalyst loss by sampling
- Automated live analysis in complicated systems
12
Source: Anal. Chem., 2010, 82 (14), pp 6008–6014

14. 13
Introduction
 Tuning the Selectivity of the Oxetane and CO2 Coupling Process
Catalyzed by (Salen)CrCl/n-Bu4NX: Cyclic Carbonate Formation vs
Aliphatic Polycarbonate Production
Donald J. Darensbourg* and Adriana I. Moncada
Department of Chemistry, Texas A&M University, College Station, Texas
77843
Source: Macromolecules, 2010, 43 (14), pp 5996–6003

15. Introduction
14
Source: Macromolecules, 2010, 43 (14), pp 5996–6003
 Biodegradable aliphatic
polycarbonates are important
components of non-toxic
thermoplastic elastomers
 Alternative copolymerization of
CO2 and aliphatic epoxide such as
propylene oxide in the presence of
metal-based catalyst has shown
significant advances
 There are economic and
environmental benefits arising from
the use of biorenewable carbon
dioxide

16. Oxetane + CO2 Copolymerization Reaction
15
Source: Macromolecules, 2010, 43 (14), pp 5996–6003
Complex 1
Oxetane (Ring Opening Polymerization)
TMC (Trimethylene Carbonate)

17. Effect of Cocatalyst Species
16
Source: Macromolecules, 2010, 43 (14), pp 5996–6003

18. TMC Formation Rates
17
Source: Macromolecules, 2010, 43 (14), pp 5996–6003

19. Poly(TMC) and TMC Formation with Temperature
18
Source: Macromolecules, 2010, 43 (14), pp 5996–6003
Poly(TMC)
TMC

20. Conclusions
 (Salen)CrCl complex along with n-Bu4NX (X = Br, I) is an
effective catalyst system for the selective coupling of
oxetane and CO2
 Provides the corresponding polycarbonate with minimal
amounts of ether linkages at 110 C
 Selectivity of the oxetane and CO2 coupling process can
be tuned by altering the nature of the anionic-based
cocatalyst
 Anions that are good leaving groups such as bromide
and iodide, are more effective at yielding trimethylene
carbonate
 Real-time in situ FTIR provided key information about
reaction rates under pressure without upsetting reaction
19
Source: Macromolecules, 2010, 43 (14), pp 5996–6003

21. 20
Introduction
 Equimolar CO2 Absorption by Anion-Functionalized Ionic Liquids
Burcu E. Gurkan, Juan C. de la Fuente,† Elaine M. Mindrup, Lindsay E.
Ficke, Brett F. Goodrich, Erica A. Price, William F. Schneider,* and Joan
F. Brennecke*
Department of Chemical and Biomolecular Engineering, University of Notre
Dame, Notre Dame, Indiana 46556
Source:: JACS 2010, 132, 2116 – 2117

22. Introduction
 Materials that selectively and efficiently absorb CO2
from flue gases is essential to realizing practical
carbon capture and sequestration
 Ionic liquids are promising because of their negligible
vapor pressures, high thermal stability and virtually
limitless chemical tunability
 Anion functionalized ionic liquids can obtain extremely
high capacity for CO2 (one mole of CO2 per mole of IL)
21
Source:: JACS 2010, 132, 2116 – 2117

23. Confirmation of 1:1 Stoichiometry
22
Source:: JACS 2010, 132, 2116 – 2117

24. CO2 Reacted with [P66614][Met]
23
Source:: JACS 2010, 132, 2116 – 2117

25. Fraction of Dissolved vs. Reacted CO2
24
Source:: JACS 2010, 132, 2116 – 2117

26. List of Additional Publications
 Organometallics 2007, 26, 1134-1142
 Org. Lett., Vol. 10, No. 13, 2008
 J. of Supercritical Fluids 46 (2008) 218–225
 Analytical Biochemistry 385 (2009) 187–193
 Applied Catalysis A: General 264 (2004) 1–12
 Inorganic Chemistry, Vol. 47, No. 21, 2008
 Inorg. Chem. 2009, 48, 7787–7793
 Chem. Mater. 2008, 20, 7022–7030
 Chemical Engineering Research and Design 87 (2009) 97–101
 J. Am. Chem. Soc. 2008, 130, 15602–15610

27. Internal usage only
Questions and Answers
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OR
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OR
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on-demand webinar library
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26