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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...
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.
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.
Zeroth Law of Thermodynamics01:14

Zeroth Law of Thermodynamics

Experimentally, if object A is in equilibrium with object B, and object B is in equilibrium with object C, then object A is in equilibrium with object C. That statement of transitivity is called the "zeroth law of thermodynamics." For example, a cold metal block and a hot metal block are both placed on a metal plate at room temperature. Eventually, the cold block and the plate will be in thermal equilibrium. In addition, the hot block and the plate will be in thermal equilibrium. By the zeroth...
Thermodynamic Potentials01:26

Thermodynamic Potentials

Thermodynamic potentials are state functions that are extremely useful in analyzing a thermodynamic system. They have dimensions of energy. The four important thermodynamic potentials are internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy. These thermodynamic potentials can be expressed using two of the following variables: pressure, volume, temperature, and entropy. These two variables are expressed as the rate of change of the thermodynamic potential with respect to other...
Joule-Thomson Effect01:21

Joule-Thomson Effect

The Joule-Thomson effect, also known as the Joule-Kelvin effect, describes the temperature change of a fluid when it is forced through a valve or porous plug while keeping it in a thermally insulated environment. This experiment is called a throttling process. This is an important effect widely used in refrigeration and the liquefaction of gases.
This experiment forces high-pressure gas through a throttle valve or a porous plug to a lower-pressure region. The gas expands as it passes through to...