Chemical kinetics

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Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry that is concerned with understanding the rates of chemical reactions. It is to be contrasted with thermodynamics, which deals with the direction in which a process occurs but in itself tells nothing about its rate. Chemical kinetics includes investigations of how experimental conditions influence the speed of a chemical reaction and yield information about the reaction's mechanism and transition states, as well as the construction of mathematical models that also can describe the characteristics of a chemical reaction.

Contents

History

In 1864, Peter Waage and Cato Guldberg pioneered the development of chemical kinetics by formulating the law of mass action, which states that the speed of a chemical reaction is proportional to the quantity of the reacting substances. [1] [2] [3]

Van 't Hoff studied chemical dynamics and in 1884 published his famous "Études de dynamique chimique". [4] In 1901 he was awarded by the first Nobel Prize in Chemistry "in recognition of the extraordinary services he has rendered by the discovery of the laws of chemical dynamics and osmotic pressure in solutions". [5] After van 't Hoff, chemical kinetics deals with the experimental determination of reaction rates from which rate laws and rate constants are derived. Relatively simple rate laws exist for zero order reactions (for which reaction rates are independent of concentration), first order reactions, and second order reactions, and can be derived for others. Elementary reactions follow the law of mass action, but the rate law of stepwise reactions has to be derived by combining the rate laws of the various elementary steps, and can become rather complex. In consecutive reactions, the rate-determining step often determines the kinetics. In consecutive first order reactions, a steady state approximation can simplify the rate law. The activation energy for a reaction is experimentally determined through the Arrhenius equation and the Eyring equation. The main factors that influence the reaction rate include: the physical state of the reactants, the concentrations of the reactants, the temperature at which the reaction occurs, and whether or not any catalysts are present in the reaction.

Gorban and Yablonsky have suggested that the history of chemical dynamics can be divided into three eras. [6] The first is the van 't Hoff wave searching for the general laws of chemical reactions and relating kinetics to thermodynamics. The second may be called the Semenov--Hinshelwood wave with emphasis on reaction mechanisms, especially for chain reactions. The third is associated with Aris and the detailed mathematical description of chemical reaction networks.

Factors affecting reaction rate

Nature of the reactants

The reaction rate varies depending upon what substances are reacting. Acid/base reactions, the formation of salts, and ion exchange are usually fast reactions. When covalent bond formation takes place between the molecules and when large molecules are formed, the reactions tend to be slower.

The nature and strength of bonds in reactant molecules greatly influence the rate of their transformation into products.

Physical state

The physical state (solid, liquid, or gas) of a reactant is also an important factor of the rate of change. When reactants are in the same phase, as in aqueous solution, thermal motion brings them into contact. However, when they are in separate phases, the reaction is limited to the interface between the reactants. Reaction can occur only at their area of contact; in the case of a liquid and a gas, at the surface of the liquid. Vigorous shaking and stirring may be needed to bring the reaction to completion. This means that the more finely divided a solid or liquid reactant the greater its surface area per unit volume and the more contact it with the other reactant, thus the faster the reaction. To make an analogy, for example, when one starts a fire, one uses wood chips and small branches — one does not start with large logs right away. In organic chemistry, on water reactions are the exception to the rule that homogeneous reactions take place faster than heterogeneous reactions ( are those reactions in which solute and solvent not mix properly)

Surface area of solid state

In a solid, only those particles that are at the surface can be involved in a reaction. Crushing a solid into smaller parts means that more particles are present at the surface, and the frequency of collisions between these and reactant particles increases, and so reaction occurs more rapidly. For example, Sherbet (powder) is a mixture of very fine powder of malic acid (a weak organic acid) and sodium hydrogen carbonate. On contact with the saliva in the mouth, these chemicals quickly dissolve and react, releasing carbon dioxide and providing for the fizzy sensation. Also, fireworks manufacturers modify the surface area of solid reactants to control the rate at which the fuels in fireworks are oxidised, using this to create diverse effects. For example, finely divided aluminium confined in a shell explodes violently. If larger pieces of aluminium are used, the reaction is slower and sparks are seen as pieces of burning metal are ejected.

Concentration

The reactions are due to collisions of reactant species. The frequency with which the molecules or ions collide depends upon their concentrations. The more crowded the molecules are, the more likely they are to collide and react with one another. Thus, an increase in the concentrations of the reactants will usually result in the corresponding increase in the reaction rate, while a decrease in the concentrations will usually have a reverse effect. For example, combustion will occur more rapidly in pure oxygen than in air (21% oxygen).

The rate equation shows the detailed dependence of the reaction rate on the concentrations of reactants and other species present. The mathematical forms depend on the reaction mechanism. The actual rate equation for a given reaction is determined experimentally and provides information about the reaction mechanism. The mathematical expression of the rate equation is often given by

Here is the reaction rate constant, is the molar concentration of reactant i and is the partial order of reaction for this reactant. The partial order for a reactant can only be determined experimentally and is often not indicated by its stoichiometric coefficient.

Temperature

Temperature usually has a major effect on the rate of a chemical reaction. Molecules at a higher temperature have more thermal energy. Although collision frequency is greater at higher temperatures, this alone contributes only a very small proportion to the increase in rate of reaction. Much more important is the fact that the proportion of reactant molecules with sufficient energy to react (energy greater than activation energy: E > Ea) is significantly higher and is explained in detail by the Maxwell–Boltzmann distribution of molecular energies.

The effect of temperature on the reaction rate constant usually obeys the Arrhenius equation , where A is the pre-exponential factor or A-factor, Ea is the activation energy, R is the molar gas constant and T is the absolute temperature. [7]

At a given temperature, the chemical rate of a reaction depends on the value of the A-factor, the magnitude of the activation energy, and the concentrations of the reactants. Usually, rapid reactions require relatively small activation energies.

The 'rule of thumb' that the rate of chemical reactions doubles for every 10 °C temperature rise is a common misconception. This may have been generalized from the special case of biological systems, where the α (temperature coefficient) is often between 1.5 and 2.5.

The kinetics of rapid reactions can be studied with the temperature jump method. This involves using a sharp rise in temperature and observing the relaxation time of the return to equilibrium. A particularly useful form of temperature jump apparatus is a shock tube, which can rapidly increase a gas's temperature by more than 1000 degrees.

Catalysts

Generic potential energy diagram showing the effect of a catalyst in a hypothetical endothermic chemical reaction. The presence of the catalyst opens a new reaction pathway (shown in red) with a lower activation energy. The final result and the overall thermodynamics are the same. Activation energy.svg
Generic potential energy diagram showing the effect of a catalyst in a hypothetical endothermic chemical reaction. The presence of the catalyst opens a new reaction pathway (shown in red) with a lower activation energy. The final result and the overall thermodynamics are the same.

A catalyst is a substance that alters the rate of a chemical reaction but it remains chemically unchanged afterwards. The catalyst increases the rate of the reaction by providing a new reaction mechanism to occur with in a lower activation energy. In autocatalysis a reaction product is itself a catalyst for that reaction leading to positive feedback. Proteins that act as catalysts in biochemical reactions are called enzymes. Michaelis–Menten kinetics describe the rate of enzyme mediated reactions. A catalyst does not affect the position of the equilibrium, as the catalyst speeds up the backward and forward reactions equally.

In certain organic molecules, specific substituents can have an influence on reaction rate in neighbouring group participation.[ citation needed ]

Pressure

Increasing the pressure in a gaseous reaction will increase the number of collisions between reactants, increasing the rate of reaction. This is because the activity of a gas is directly proportional to the partial pressure of the gas. This is similar to the effect of increasing the concentration of a solution.

In addition to this straightforward mass-action effect, the rate coefficients themselves can change due to pressure. The rate coefficients and products of many high-temperature gas-phase reactions change if an inert gas is added to the mixture; variations on this effect are called fall-off and chemical activation. These phenomena are due to exothermic or endothermic reactions occurring faster than heat transfer, causing the reacting molecules to have non-thermal energy distributions (non-Boltzmann distribution). Increasing the pressure increases the heat transfer rate between the reacting molecules and the rest of the system, reducing this effect.

Condensed-phase rate coefficients can also be affected by pressure, although rather high pressures are required for a measurable effect because ions and molecules are not very compressible. This effect is often studied using diamond anvils.

A reaction's kinetics can also be studied with a pressure jump approach. This involves making fast changes in pressure and observing the relaxation time of the return to equilibrium.

Absorption of light

The activation energy for a chemical reaction can be provided when one reactant molecule absorbs light of suitable wavelength and is promoted to an excited state. The study of reactions initiated by light is photochemistry, one prominent example being photosynthesis.

Experimental methods

The Spinco Division Model 260 Reaction Kinetics System measured the precise rate constants of molecular reactions. Reaction kinetics system nz805z932.tiff
The Spinco Division Model 260 Reaction Kinetics System measured the precise rate constants of molecular reactions.

The experimental determination of reaction rates involves measuring how the concentrations of reactants or products change over time. For example, the concentration of a reactant can be measured by spectrophotometry at a wavelength where no other reactant or product in the system absorbs light.

For reactions which take at least several minutes, it is possible to start the observations after the reactants have been mixed at the temperature of interest.

Fast reactions

For faster reactions, the time required to mix the reactants and bring them to a specified temperature may be comparable or longer than the half-life of the reaction. [8] Special methods to start fast reactions without slow mixing step include

Equilibrium

While chemical kinetics is concerned with the rate of a chemical reaction, thermodynamics determines the extent to which reactions occur. In a reversible reaction, chemical equilibrium is reached when the rates of the forward and reverse reactions are equal (the principle of dynamic equilibrium) and the concentrations of the reactants and products no longer change. This is demonstrated by, for example, the Haber–Bosch process for combining nitrogen and hydrogen to produce ammonia. Chemical clock reactions such as the Belousov–Zhabotinsky reaction demonstrate that component concentrations can oscillate for a long time before finally attaining the equilibrium.

Free energy

In general terms, the free energy change (ΔG) of a reaction determines whether a chemical change will take place, but kinetics describes how fast the reaction is. A reaction can be very exothermic and have a very positive entropy change but will not happen in practice if the reaction is too slow. If a reactant can produce two products, the thermodynamically most stable one will form in general, except in special circumstances when the reaction is said to be under kinetic reaction control. The Curtin–Hammett principle applies when determining the product ratio for two reactants interconverting rapidly, each going to a distinct product. It is possible to make predictions about reaction rate constants for a reaction from free-energy relationships.

The kinetic isotope effect is the difference in the rate of a chemical reaction when an atom in one of the reactants is replaced by one of its isotopes.

Chemical kinetics provides information on residence time and heat transfer in a chemical reactor in chemical engineering and the molar mass distribution in polymer chemistry. It is also provides information in corrosion engineering.

Applications and models

The mathematical models that describe chemical reaction kinetics provide chemists and chemical engineers with tools to better understand and describe chemical processes such as food decomposition, microorganism growth, stratospheric ozone decomposition, and the chemistry of biological systems. These models can also be used in the design or modification of chemical reactors to optimize product yield, more efficiently separate products, and eliminate environmentally harmful by-products. When performing catalytic cracking of heavy hydrocarbons into gasoline and light gas, for example, kinetic models can be used to find the temperature and pressure at which the highest yield of heavy hydrocarbons into gasoline will occur.

Chemical Kinetics is frequently validated and explored through modeling in specialized packages as a function of ordinary differential equation-solving (ODE-solving) and curve-fitting. [17]

Examples of specialized packages for chemical kinetic modeling include: MultiWell suite, [18] Reaction Mechanism Generator (RMG) suite, [19] and KinBot. [20]

Related Research Articles

In a chemical reaction, chemical equilibrium is the state in which both reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the system. Usually, this state results when the forward reaction proceeds at the same rate as the reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but equal. Thus, there are no net changes in the concentrations of the reactant(s) and product(s). Such a state is known as dynamic equilibrium.

Catalysis chemical process

Catalysis is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst, which is not consumed in the catalyzed reaction and can continue to act repeatedly. Because of this, only very small amounts of catalyst are required to alter the reaction rate in most cases.

Chemical reaction Process that results in the interconversion of chemical species

A chemical reaction is a process that leads to the chemical transformation of one set of chemical substances to another. Classically, chemical reactions encompass changes that only involve the positions of electrons in the forming and breaking of chemical bonds between atoms, with no change to the nuclei, and can often be described by a chemical equation. Nuclear chemistry is a sub-discipline of chemistry that involves the chemical reactions of unstable and radioactive elements where both electronic and nuclear changes can occur.

Le Chatelier's principle, also called Chatelier's principle or "The Equilibrium Law", is a principle of chemistry used to predict the effect of a change in conditions on chemical equilibria. The principle is named after French chemist Henry Louis Le Chatelier, and sometimes also credited to Karl Ferdinand Braun, who discovered it independently. It can be stated as:

When any system at equilibrium for a long period of time is subjected to a change in concentration, temperature, volume, or pressure, (1) the system changes to a new equilibrium, and (2) this change partly counteracts the applied change.

Activation energy Energy that must be input to a system to undergo a reaction or process

In chemistry and physics, activation energy is the energy which must be provided to a chemical or nuclear system with potential reactants to result in: a chemical reaction, nuclear reaction, or various other physical phenomena.

In physical chemistry, the Arrhenius equation is a formula for the temperature dependence of reaction rates. The equation was proposed by Svante Arrhenius in 1889, based on the work of Dutch chemist Jacobus Henricus van 't Hoff who had noted in 1884 that van 't Hoff equation for the temperature dependence of equilibrium constants suggests such a formula for the rates of both forward and reverse reactions. This equation has a vast and important application in determining rate of chemical reactions and for calculation of energy of activation. Arrhenius provided a physical justification and interpretation for the formula. Currently, it is best seen as an empirical relationship. It can be used to model the temperature variation of diffusion coefficients, population of crystal vacancies, creep rates, and many other thermally-induced processes/reactions. The Eyring equation, developed in 1935, also expresses the relationship between rate and energy.

Reaction rate for a reactant or product in a particular reaction is intuitively defined as how quickly or slowly a reaction takes place

The reaction rate or rate of reaction is the speed at which reactants are converted into products. For example, the oxidative rusting of iron under Earth's atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second. For most reactions, the rate decreases as the reaction proceeds.

A single chemical reaction is said to be autocatalytic if one of the reaction products is also a catalyst for the same or a coupled reaction. Such a reaction is called an autocatalytic reaction.

In chemistry, reactivity is the impetus for which a chemical substance undergoes a chemical reaction, either by itself or with other materials, with an overall release of energy.

In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs.

In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate-determining step (RDS) or rate-limiting step. For a given reaction mechanism, the prediction of the corresponding rate equation is often simplified by using this approximation of the rate-determining step.

Collision theory

Collision theory states that when suitable particles of the reactant hit each other, only a certain fraction of the collisions cause any noticeable or significant chemical change; these successful changes are called successful collisions. The successful collisions must have enough energy, also known as activation energy, at the moment of impact to break the pre-existing bonds and form all new bonds. This results in the products of the reaction. Increasing the concentration of the reactant brings about more collisions and hence more successful collisions. Increasing the temperature increases the average kinetic energy of the molecules in a solution, increasing the collisions that have enough energy. Collision theory was proposed independently by Max Trautz in 1916 and William Lewis in 1918.

In chemical kinetics a reaction rate constant or reaction rate coefficient, k, quantifies the rate of a chemical reaction.

Molecularity in chemistry is the number of molecules that come together to react in an elementary (single-step) reaction and is equal to the sum of stoichiometric coefficients of reactants in this elementary reaction. Depending on how many molecules come together, a reaction can be unimolecular, bimolecular or trimolecular.

Transition state theory scientific theory

Transition state theory (TST) explains the reaction rates of elementary chemical reactions. The theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and activated transition state complexes.

Physical organic chemistry, a term coined by Louis Hammett in 1940, refers to a discipline of organic chemistry that focuses on the relationship between chemical structures and reactivity, in particular, applying experimental tools of physical chemistry to the study of organic molecules. Specific focal points of study include the rates of organic reactions, the relative chemical stabilities of the starting materials, reactive intermediates, transition states, and products of chemical reactions, and non-covalent aspects of solvation and molecular interactions that influence chemical reactivity. Such studies provide theoretical and practical frameworks to understand how changes in structure in solution or solid-state contexts impact reaction mechanism and rate for each organic reaction of interest.

Energy profile (chemistry)

For a chemical reaction or process an energy profile is a theoretical representation of a single energetic pathway, along the reaction coordinate, as the reactants are transformed into products. Reaction coordinate diagrams are derived from the corresponding potential energy surface (PES), which are used in computational chemistry to model chemical reactions by relating the energy of a molecule(s) to its structure. The reaction coordinate is a parametric curve that follows the pathway of a reaction and indicates the progress of a reaction.

In chemistry, solvent effects are the influence of a solvent on chemical reactivity or molecular associations. Solvents can have an effect on solubility, stability and reaction rates and choosing the appropriate solvent allows for thermodynamic and kinetic control over a chemical reaction.

The first time a catalyst was used in the industry was in 1746 by J. Hughes in the manufacture of lead chamber sulfuric acid. Since then catalysts have been in use in a large portion of the chemical industry. In the start only pure components were used as catalysts, but after the year 1900 multicomponent catalysts were studied and are now commonly used in the industry.

In 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 in the late 1990s and has since seen increasingly widespread use. Unlike more common pseudo-first-order analysis, in which an overwhelming excess of one or more reagents is used relative to a species of interest, RPKA probes reactions at synthetically relevant conditions Generally, this analysis involves a system in which the concentrations of multiple reactants are changing measurably over the course of the reaction. As the mechanism can vary depending on the relative and absolute concentrations of the species involved, this approach obtains results that are much more representative of reaction behavior under commonly utilized conditions than do traditional tactics. Furthermore, information obtained by observation of the reaction over time may provide insight regarding unexpected behavior such as induction periods, catalyst deactivation, or changes in mechanism.

References

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  3. C.M. Guldberg, "Concerning the Laws of Chemical Affinity", Forhandlinger i Videnskabs-Selskabet i Christiania (1864) 111
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  16. Steinfeld J.I., Francisco J.S. and Hase W.L. Chemical Kinetics and Dynamics (2nd ed., Prentice-Hall 1999) p.94-97 ISBN   0-13-737123-3
  17. "Chemical Kinetics: Simple Binding: F + G ⇋ B" (PDF). Civilized Software, Inc. Retrieved 2015-09-01.
  18. "MultiWell Program Suite > Homepage | University of Michigan". clasp-research.engin.umich.edu. Retrieved 2020-04-08.
  19. "RMG - Reaction Mechanism Generator". rmg.mit.edu. Retrieved 2020-04-08.
  20. "Sandia National Laboratories: KinBot". kinbot.sandia.gov. Retrieved 2020-04-08.

See also