Partial pressureIn a mixture of gases, each constituent gas has a partial pressure which is the notional pressure of that constituent gas as if it alone occupied the entire volume of the original mixture at the same temperature. The total pressure of an ideal gas mixture is the sum of the partial pressures of the gases in the mixture (Dalton's Law). The partial pressure of a gas is a measure of thermodynamic activity of the gas's molecules. Gases dissolve, diffuse, and react according to their partial pressures but not according to their concentrations in gas mixtures or liquids.
Rate-determining stepIn chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS or RD-step or r/d step) or rate-limiting step. For a given reaction mechanism, the prediction of the corresponding rate equation (for comparison with the experimental rate law) is often simplified by using this approximation of the rate-determining step. In principle, the time evolution of the reactant and product concentrations can be determined from the set of simultaneous rate equations for the individual steps of the mechanism, one for each step.
Heterogeneous catalysisHeterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. Phase distinguishes between not only solid, liquid, and gas components, but also immiscible mixtures (e.g. oil and water), or anywhere an interface is present. Heterogeneous catalysis typically involves solid phase catalysts and gas phase reactants.
Reaction progress kinetic analysisIn chemistry, reaction progress kinetic analysis (RPKA) is a subset of a broad range of kinetic techniques utilized to determine the rate laws of chemical reactions and to aid in elucidation of reaction mechanisms. While the concepts guiding reaction progress kinetic analysis are not new, the process was formalized by Professor Donna Blackmond (currently at Scripps Research Institute) in the late 1990s and has since seen increasingly widespread use.
Half-lifeHalf-life (symbol t_1⁄2) is the time required for a quantity (of substance) to reduce to half of its initial value. The term is commonly used in nuclear physics to describe how quickly unstable atoms undergo radioactive decay or how long stable atoms survive. The term is also used more generally to characterize any type of exponential (or, rarely, non-exponential) decay. For example, the medical sciences refer to the biological half-life of drugs and other chemicals in the human body.
MetastabilityIn chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy. A ball resting in a hollow on a slope is a simple example of metastability. If the ball is only slightly pushed, it will settle back into its hollow, but a stronger push may start the ball rolling down the slope. Bowling pins show similar metastability by either merely wobbling for a moment or tipping over completely. A common example of metastability in science is isomerisation.
Entropy of activationIn chemical kinetics, the entropy of activation of a reaction is one of the two parameters (along with the enthalpy of activation) which are typically obtained from the temperature dependence of a reaction rate constant, when these data are analyzed using the Eyring equation of the transition state theory. The standard entropy of activation is symbolized ΔS‡ and equals the change in entropy when the reactants change from their initial state to the activated complex or transition state (Δ = change, S = entropy, ‡ = activation).
Water–gas shift reactionThe water–gas shift reaction (WGSR) describes the reaction of carbon monoxide and water vapor to form carbon dioxide and hydrogen: CO + H2O CO2 + H2 The water gas shift reaction was discovered by Italian physicist Felice Fontana in 1780. It was not until much later that the industrial value of this reaction was realized. Before the early 20th century, hydrogen was obtained by reacting steam under high pressure with iron to produce iron oxide and hydrogen.
Reactive intermediateIn chemistry, a reactive intermediate or an intermediate is a short-lived, high-energy, highly reactive molecule. When generated in a chemical reaction, it will quickly convert into a more stable molecule. Only in exceptional cases can these compounds be isolated and stored, e.g. low temperatures, matrix isolation. When their existence is indicated, reactive intermediates can help explain how a chemical reaction takes place.
Lindemann mechanismIn chemical kinetics, the Lindemann mechanism (also called the Lindemann–Christiansen mechanism or the Lindemann–Hinshelwood mechanism) is a schematic reaction mechanism for unimolecular reactions. Frederick Lindemann and J. A. Christiansen proposed the concept almost simultaneously in 1921, and Cyril Hinshelwood developed it to take into account the energy distributed among vibrational degrees of freedom for some reaction steps. It breaks down an apparently unimolecular reaction into two elementary steps, with a rate constant for each elementary step.
