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Mass Spectrometry: Isotope Effect01:13

Mass Spectrometry: Isotope Effect

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Most elements exist in nature as a mixture of isotopes. The isotopes differ in weight due to their respective number of neutrons. The molecular weight of a molecule is different depending on the specific isotope of its elements involved. As a result, the mass spectrum of the molecule exhibits peaks from the same fragment at multiple positions. The positions of these mass signals depend on the difference between the molecular mass. Furthermore, the intensity of these signals is dependent on the...
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Isotopes01:12

Isotopes

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Elements have a set number of protons that determines their atomic number (Z). For example, all atoms with eight protons are oxygen; however, the number of neutrons can vary for atoms of the same element. The sum of the number of protons and the number of neutrons is the mass number (A). Atoms with the same atomic number but different mass numbers are called isotopes. Elements can have multiple isotopes, for example, carbon-12, carbon-13, and carbon-14.
An element's atomic mass, or weight,...
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Isotopes and Radioisotopes01:28

Isotopes and Radioisotopes

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In the early 1900s, English chemist Frederick Soddy realized that an element could have atoms with different masses that were chemically indistinguishable. These different types are called isotopes — atoms of the same element that differ in mass. Isotopes differ in mass because they have different numbers of neutrons but are chemically identical because they have the same number of protons. Soddy was awarded the Nobel Prize in Chemistry in 1921 for this discovery.
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¹H NMR of Labile Protons: Deuterium (²H) Substitution00:48

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This lesson illustrates the role of deuterium substitution in simplifying the NMR spectrum of compounds comprising labile protons. One method employed is the use of deuterium. Amongst the three isotopes of hydrogen, deuterium (2H) has a nucleus composed of one proton and one neutron. When the D2O solvent is added to a pure dry ethanol solution, its labile proton is substituted with deuterium.
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Nuclear Overhauser Enhancement (NOE)01:07

Nuclear Overhauser Enhancement (NOE)

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Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling.  This phenomenon, called the Nuclear Overhauser Enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring...
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Atomic Nuclei: Nuclear Spin State Population Distribution01:14

Atomic Nuclei: Nuclear Spin State Population Distribution

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Near absolute zero temperatures, in the presence of a magnetic field, the majority of nuclei prefer the lower energy spin-up state to the higher energy spin-down state. As temperatures increase, the energy from thermal collisions distributes the spins more equally between the two states. The Boltzmann distribution equation gives the ratio of the number of spins predicted in the spin −½ (N−) and spin +½ (N+) states.
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Isotope Effect in D

Sarvesh Kumar1, Masamitsu Hoshino2, Boutheïna Kerkeni3,4

  • 1Atomic and Molecular Collisions Laboratory, CEFITEC, Department of Physics, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal.

The Journal of Physical Chemistry Letters
|June 5, 2023
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Summary
This summary is machine-generated.

Investigating electron transfer in H2O/D2O collisions with potassium reveals energy-dependent branching ratios and isotope effects. This study determines the D-O bond dissociation energy for D2O for the first time.

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Area of Science:

  • Physical Chemistry
  • Chemical Physics
  • Atomic and Molecular Collisions

Background:

  • Understanding electron transfer processes in molecules is crucial for chemical dynamics.
  • Water (H2O) and its isotopologue (D2O) are fundamental molecules in chemistry and physics.
  • Investigating ion-molecule reactions provides insights into molecular electronic structures.

Purpose of the Study:

  • To investigate electron transfer processes in H2O/D2O collisions with neutral potassium.
  • To determine the energy dependence of branching ratios and isotope effects.
  • To characterize the electronic states and bond dissociation energies involved.

Main Methods:

  • Time-of-flight mass spectrometry of negative ions (OH-/OD-, O-, H-/D-) from H2O/D2O collisions with potassium.
  • Potassium cation energy loss spectroscopy at 205 eV impact energy.
  • Quantum chemical calculations for unoccupied molecular orbitals in K-H2O/D2O systems.

Main Results:

  • Observed OH-/OD-, O-, and H-/D- negative ions, with energy-dependent branching ratios.
  • Significant isotope effect observed in D2O collisions.
  • Determined the D-O bond dissociation energy of D2O to be 5.41 ± 0.10 eV.
  • Supported experimental findings with quantum chemical calculations, identifying electronic states involved.

Conclusions:

  • Electron transfer collisions of H2O/D2O with potassium exhibit significant energy dependence and isotope effects.
  • The study provides the first experimental determination of the D-O bond dissociation energy in D2O.
  • Collision dynamics elucidate the nature of singly and doubly excited molecular orbitals in K-H2O/D2O systems.