Kinetic Thermodynamic Products

Kinetic and thermodynamic products are alternative products formed when a reaction can proceed through competing pathways, with their relative amounts determined by reaction rate and product stability. Under kinetic control, the product that forms fastest through the pathway with the lower activation energy predominates, often at lower temperatures or with short reaction times; under thermodynamic control, reversible reactions favor the more stable product when conditions allow interconversion and equilibration. Understanding this distinction helps chemists predict reaction selectivity, choose appropriate temperature and time conditions, and optimize synthetic routes involving competing addition, substitution, or elimination products.

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JoVE Core - Chemistry

Third Law of Thermodynamics

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2020

A pure, perfectly crystalline solid possessing no kinetic energy (that is, at a temperature of absolute zero, 0 K) may be described by a single microstate, as its purity, perfect crystallinity,and complete lack of motion means there is but one possible location for each identical atom or molecule comprising the crystal (W = 1). According to the Boltzmann equation, the entropy of this system is zero. This limiting condition for a system’s entropy represents the third law of thermodynamics: the...

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JoVE Core - Chemistry
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First Law of Thermodynamics

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2020

Energy Conservation Energy can be converted from one form into another, but all of the energy present before a change occurs always exists in some form after the change is completed. This observation is expressed in the law of conservation of energy: during a chemical or physical change, energy can be neither created nor destroyed, although it can be changed in form. According to the law of conservation of matter, there is no detectable change in the total amount of matter during a chemical...

Second Law of Thermodynamics

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2020

In the quest to identify a property that may reliably predict the spontaneity of a process, a promising candidate has been identified: entropy. Processes that involve an increase in entropy of the system (ΔS > 0) are very often spontaneous; however, examples to the contrary are plentiful. By expanding consideration of entropy changes to include the surroundings, a significant conclusion regarding the relation between this property and spontaneity may be reached. In thermodynamic models, the...

Electrophilic Addition of HX to 1,3-Butadiene: Thermodynamic vs Kinetic Control

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2023

The addition of a hydrogen halide to 1,3-butadiene gives a mixture of 1,2- and 1,4-adducts. Since more substituted alkenes are more stable, the 1,4-adduct is expected to be the major product. However, the product distribution is strongly influenced by temperature; low temperature favors the 1,2-adduct, whereas the 1,4-adduct is predominant at high temperature. At lower temperatures, the two products are not in equilibrium. Under these conditions, the product distribution depends on the...

Enzyme Assays and Kinetics

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2023

Enzyme kinetics describes the catalytic effects of enzymes, which are biomolecules that facilitate chemical reactions necessary for living organisms. Enzymes act on molecules, referred to as substrates, to form products. Enzyme kinetic parameters are determined via assays that directly or indirectly measure changes in substrate or product concentration over time. This video will cover the basic principles of enzyme kinetics (including rate equations) and kinetic models. The concepts governing...

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