Stochastic transitions through unstable limit cycles in a model of bistable thermochemical system

Andrzej L Kawczyński1, Bogdan Nowakowski

  • 1Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, Warsaw, Poland.

Related Concept Videos

Transition State Theory01:25

Transition State Theory

Transition-state theory, also known as activated-complex theory, provides a molecular-level explanation of reaction rates in both gas-phase and solution-phase reactions. It extends earlier kinetic models by considering the formation of a short-lived, high-energy configuration during a reaction.The progress of a chemical reaction can be represented using a reaction profile, which plots potential energy against the reaction coordinate. As two reactant molecules approach one another, their...
The Entropy as a State Function01:14

The Entropy as a State Function

Consider an arbitrary process that moves between two specific states (A and B) in a cyclic manner. This process is reversible and broken down into smaller parts that each follow a Carnot cycle. A Carnot cycle has two isothermal (constant temperature) processes. During these processes, the ratio of the amount of heat transferred to their respective temperature remains constant. The other two processes in the Carnot cycle are also reversible but adiabatic, which means they occur without any heat...
Second Law of Thermodynamics02:49

Second Law of Thermodynamics

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...
Second Law of Thermodynamics00:53

Second Law of Thermodynamics

The Second Law of Thermodynamics states that entropy, or the amount of disorder in a system, increases each time energy is transferred or transformed. Each energy transfer results in a certain amount of energy that is lost—usually in the form of heat—that increases the disorder of the surroundings. This can also be demonstrated in a classic food web. Herbivores harvest chemical energy from plants and release heat and carbon dioxide into the environment. Carnivores harvest the chemical energy...
Entropy Change in Reversible Processes01:10

Entropy Change in Reversible Processes

In the Carnot engine, which achieves the maximum efficiency between two reservoirs of fixed temperatures, the total change in entropy is zero. The observation can be generalized by considering any reversible cyclic process consisting of many Carnot cycles. Thus, it can be stated that the total entropy change of any ideal reversible cycle is zero.
The statement can be further generalized to prove that entropy is a state function. Take a cyclic process between any two points on a p-V diagram.
Phase Transitions01:21

Phase Transitions

A phase transition is the process in which a substance changes from one state of matter to another, like from a solid to a liquid, liquid to gas, or vice versa, at a specific temperature and under given pressure conditions. This change is spontaneous and is affected by alterations in temperature and pressure. These parameters impact the strength of the forces between molecules (intermolecular forces) in the substance.During a phase transition, both the initial and final phases of the substance...