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Spectroscopy of Carboxylic Acid Derivatives01:26

Spectroscopy of Carboxylic Acid Derivatives

Infrared spectroscopy is primarily used to determine the types of bonds and functional groups. In carboxylic acid derivatives, a typical carbonyl bond absorption is observed around 1650–1850 cm−1. For esters, the absorption is recorded at around 1740 cm−1, while acid halides show the absorption at about 1800 cm−1. Another acid derivative, the acid anhydrides, exhibit two carbonyl absorption around 1760 cm−1 and 1820 cm−1, arising from the symmetrical and unsymmetrical carbonyl vibration.
In the...
¹H NMR of Conformationally Flexible Molecules: Temporal Resolution00:52

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
¹³C NMR: ¹H–¹³C Decoupling01:04

¹³C NMR: ¹H–¹³C Decoupling

The probability of having two carbon-13 atoms next to each other is negligible because of the low natural abundance of carbon-13. Consequently, peak splitting due to carbon-carbon spin-spin coupling is not observed in spectra. However, protons up to three sigma bonds away split the carbon signal according to the n+1 rule, resulting in complicated spectra.
A broadband decoupling technique is used to simplify these complex, sometimes overlapping, signals. Broadband decoupling relies on a...
¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR01:15

¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR

The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
NMR Spectroscopy of Aromatic Compounds01:14

NMR Spectroscopy of Aromatic Compounds

Aromatic compounds can be identified or analyzed using proton NMR and carbon‐13 NMR. Typically, aromatic hydrogens or hydrogens directly bonded to the aromatic rings are strongly deshielded by the aromatic ring current. Therefore, they absorb in the range of 6.5–8.0 ppm in proton NMR spectra. For instance, aromatic hydrogens directly bonded to the benzene ring absorb at 7.3 ppm. However, aromatic hydrogens of larger rings absorb farther upfield or downfield than the ideal range. Consider...
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.

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Related Experiment Video

Updated: Jun 11, 2026

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
11:42

Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers

Published on: June 20, 2019

Study of epsilon-caprolactone polymerization by NIR spectroscopy.

Marcelo Blanco1, M Jesús Sánchez, Manel Alcalà

  • 1Grup de Quimiometria Aplicada, Departament de Química (Unitat Analítica), Facultat de Ciències, Universitat Autònoma de Barcelona, 01893 Bellaterra, Barcelona, Spain.

Analytical and Bioanalytical Chemistry
|July 1, 2010
PubMed
Summary

Near-infrared (NIR) spectroscopy enables real-time monitoring of epsilon-caprolactone polymerization. This method, using multivariate curve resolution alternating least squares (MCR-ALS), accurately determines reaction kinetics without reference concentrations.

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Area of Science:

  • Polymer Chemistry
  • Spectroscopy
  • Chemical Engineering

Background:

  • Real-time process monitoring is crucial for efficient polymer manufacturing.
  • Traditional methods for studying polymerization kinetics can be time-consuming and invasive.
  • Developing non-invasive, in-line analytical techniques is essential for process optimization.

Purpose of the Study:

  • To propose and validate near-infrared (NIR) spectroscopy for in-line, quantitative, and kinetic studies of epsilon-caprolactone polymerization.
  • To facilitate real-time control of the polymerization manufacturing process.
  • To develop a method for calculating reaction kinetics without requiring reference concentrations.

Main Methods:

  • Acquisition of NIR spectra using a fiber-optic probe in transflectance mode immersed in the reactor.
  • Processing NIR data with multivariate curve resolution alternating least squares (MCR-ALS) algorithm.
  • Applying kinetic constraints (hard modeling) to improve kinetic fitting and data analysis.

Main Results:

  • Successful calculation of concentration and spectral profiles of reacting species.
  • Demonstration of MCR-ALS without the need for reference concentrations.
  • Accurate calculation of reaction rate constants and energy of activation at various temperatures.
  • Good correlation between NIR data and reference data, indicating high-quality kinetic information.

Conclusions:

  • NIR spectroscopy combined with MCR-ALS and hard modeling provides a robust method for in-line kinetic studies of polymerization.
  • The developed technique allows for real-time process monitoring and control.
  • This approach offers a valuable tool for optimizing epsilon-caprolactone polymerization processes.