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Thermochemical Equations02:55

Thermochemical Equations

30.1K
For a chemical reaction (the system) carried out at constant pressure – with the only work done caused by expansion or contraction – the enthalpy of reaction (also called the heat of reaction, ΔHrxn) is equal to the heat exchanged with the surroundings (qp).
30.1K
Hess's Law03:40

Hess's Law

46.5K
There are two ways to determine the amount of heat involved in a chemical change: measure it experimentally, or calculate it from other experimentally determined enthalpy changes. Some reactions are difficult, if not impossible, to investigate and make accurate measurements for experimentally. And even when a reaction is not hard to perform or measure, it is convenient to be able to determine the heat involved in a reaction without having to perform an experiment.
46.5K
Thermodynamic Potentials01:26

Thermodynamic Potentials

989
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...
989
Atomic Spectroscopy: Effects of Temperature01:27

Atomic Spectroscopy: Effects of Temperature

484
Atomization, converting samples into gas-phase atoms and ions, is essential for atomic spectroscopy. The flame temperature required for atomization affects the efficiency of the atomic spectroscopic methods by increasing the atomization efficiency and the relative population of the excited and ground states.
At thermal equilibrium, the relative populations of excited and ground state atoms can be estimated using the Maxwell–Boltzmann distribution. For example, an increase in temperature...
484
Thermodynamics: Chemical Potential and Activity01:10

Thermodynamics: Chemical Potential and Activity

1.2K
The effective concentration of a species in a solution can be expressed precisely in terms of its activity. Activity considers the effect of electrolytes present in the vicinity of the species of interest and depends on the ionic strength of the solution. The activity of a species is expressed as the product of molar concentration and the activity coefficient of the species.
The thermodynamic equilibrium constant is more accurately defined in terms of activity rather than concentration.
1.2K
Atomic Absorption Spectroscopy: Atomization Methods01:25

Atomic Absorption Spectroscopy: Atomization Methods

682
Atomic Absorption Spectroscopy (AAS) atomizes samples through flame atomization or electrothermal atomization. Flame atomization typically involves a nebulizer and spray chamber assembly to combine the sample with a fuel–oxidant mixture, creating a fine aerosol mist that enters a burner. Typically, the fuel and oxidant are combined in an approximately stoichiometric ratio. However, for atoms that are easily oxidized, a fuel-rich mixture may be more advantageous. Only about 5% of the...
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Related Experiment Video

Updated: Sep 21, 2025

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry
16:11

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Published on: June 8, 2022

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ATOMIC-2 Protocol for Thermochemistry.

Dirk Bakowies1

  • 1Institute of Physical Chemistry, Department of Chemistry, University of Basel, Klingelbergstraße 80, CH 4056 Basel, Switzerland.

Journal of Chemical Theory and Computation
|June 6, 2022
PubMed
Summary
This summary is machine-generated.

The ATOMIC-2 computational protocol refines thermochemistry calculations for atomization energies using bond separation reactions. Its updated error and uncertainty model (ATOMIC-2um) improves accuracy and reliability for chemical compounds.

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Area of Science:

  • Computational Chemistry
  • Theoretical Chemistry
  • Thermochemistry

Background:

  • The ATOMIC protocol utilizes bond separation reactions (BSRs) to reduce computational cost for calculating atomization energies and enthalpies of formation.
  • Existing composite models balance accuracy and computational expense, approximating bond separation energies at the complete-basis-set limit.

Purpose of the Study:

  • To introduce ATOMIC-2, an improved version of the thermochemistry protocol.
  • To enhance accuracy and computational efficiency through refined methods and an integrated error and uncertainty model (ATOMIC-2um).

Main Methods:

  • Geometry optimization and zero-point-energy calculations are performed using density functional theory (PBE0-D3/6-311G(d)).
  • Improved complete-basis-set (CBS) extrapolations towards the Full CI limit are used for auxiliary molecule atomization energies.
  • An error and uncertainty model (ATOMIC-2um) is developed to estimate bias and uncertainty in energy contributions.

Main Results:

  • ATOMIC-2 demonstrates significant computational savings and improved accuracy compared to previous methods.
  • The bias-corrected ATOMIC-2um protocol shows higher accuracy than ATOMIC-1 and Gaussian-4 theory, with a consistent uncertainty model.
  • The framework is extended to include challenging bond topologies, considering neutral, closed-shell molecules with H, C, N, O, and F atoms.

Conclusions:

  • ATOMIC-2, particularly with the ATOMIC-2um uncertainty model, offers a more accurate and reliable approach to thermochemical calculations.
  • The protocol addresses limitations of previous methods by incorporating advanced computational techniques and robust error estimation.
  • The developed computational code is made available for performing ATOMIC-2um analyses.