Temperature Jump
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Temperature Jump
The temperature jump method is a technique used in chemical kinetics for the measurement of very rapid reaction rates. It is one of a class of chemical relaxation methods pioneered by the German physical chemist Manfred Eigen in the 1950s. In these methods, a reacting system initially at equilibrium is perturbed rapidly and then observed as it ''relaxes'' back to equilibrium.Atkins P. and de Paula J. ''Atkins' Physical Chemistry'' (8th ed., W.H.Freeman 2006) p.805, Steinfeld J.I., Francisco J.S. and Hase W.L., ''Chemical Kinetics and Dynamics'' (2nd ed., Prentice-Hall 1998) p.140-3, In the case of temperature jump, the perturbation involves rapid heating which changes the value of the equilibrium constant, followed by relaxation to equilibrium at the new temperature. The heating usually involves discharging of a capacitor (in the kV range) through a small volume (< 1 mL) of a conducting solution containing the molecule/reaction to be studied. In some versions of the apparatus use ...
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Chemical Kinetics
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 chemical thermodynamics, which deals with the direction in which a reaction 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. 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.C.M. Guldberg and P. Waage,"Studies Concerning Affinity" ''Forhandlinger i Videnskabs-Selskabet i Christiania'' (1864), 35P. W ...
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Reaction Rate
The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit time. Reaction rates can vary dramatically. 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 reaction's rate can be determined by measuring the changes in concentration over time. Chemical kinetics is the part of physical chemistry that concerns how rates of chemical reactions are measured and predicted, and how reaction-rate data can be used to deduce probable reaction mechanisms. The concepts of chemical kinetics are applied in many disciplines, such as chemical engineering, enzymology and environmental engin ...
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Relaxation (physics)
In the physical sciences, relaxation usually means the return of a perturbed system into equilibrium. Each relaxation process can be categorized by a relaxation time τ. The simplest theoretical description of relaxation as function of time ''t'' is an exponential law (exponential decay A quantity is subject to exponential decay if it decreases at a rate proportional to its current value. Symbolically, this process can be expressed by the following differential equation, where is the quantity and (lambda) is a positive rate ...). In simple linear systems Mechanics: Damped unforced oscillator Let the homogeneous differential equation: :m\frac+\gamma\frac+ky=0 model damped harmonic oscillator, damped unforced oscillations of a weight on a spring. The displacement will then be of the form y(t) = A e^ \cos(\mu t - \delta). The constant T (=2m/\gamma) is called the relaxation time of the system and the constant μ is the quasi-frequency. Electronics: RC circuit In an RC ...
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Manfred Eigen
Manfred Eigen (; 9 May 1927 – 6 February 2019) was a German Biophysical chemistry, biophysical chemist who won the 1967 Nobel Prize in Chemistry for work on measuring fast chemical reactions. Eigen's research helped solve major problems in physical chemistry and aided in the understanding of chemical processes that occur in living organisms. In later years, he explored the biochemical roots of life and evolution. He worked to install a multidisciplinary program at the Max Planck Institute to study the underpinnings of life at the molecular level. His work was hailed for creating a new scientific and technological discipline: evolutionary biotechnology. Education and early life Eigen was born on 9 May 1927 in Bochum, the son of Hedwig (Feld) and Ernst Eigen, a chamber musician. As a child he developed a deep passion for music, and studied piano. World War II interrupted his formal education. At age fifteen he was drafted into service in a German antiaircraft unit. He was ca ...
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Keith J
Keith may refer to: People and fictional characters * Keith (given name), includes a list of people and fictional characters * Keith (surname) * Keith (singer), American singer James Keefer (born 1949) * Baron Keith, a line of Scottish barons in the late 18th century * Clan Keith, a Scottish clan associated with lands in northeastern and northwestern Scotland Places Australia * Keith, South Australia, a town and locality Scotland * Keith, Moray, a town ** Keith railway station * Keith Marischal, East Lothian United States * Keith, Georgia, an unincorporated community * Keith, Ohio, an unincorporated community * Keith, West Virginia, an unincorporated community * Keith, Wisconsin, a ghost town * Keith County, Nebraska Other uses * Keith F.C., a football team based in Keith, Scotland * , a ship of the British Royal Navy * Hurricane Keith, a 2000 hurricane that caused extensive damage in Central America * ''Keith'' (film), a 2008 independent film directed by Todd Kessler * ' ...
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Equilibrium Constant
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at equilibrium. However, reaction parameters like temperature, solvent, and ionic strength may all influence the value of the equilibrium constant. A knowledge of equilibrium constants is essential for the understanding of many chemical systems, as well as biochemical processes such as oxygen transport by hemoglobin in blood and acid–base homeostasis in the human body. Stability constants, formation cons ...
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Absorption Spectroscopy
Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum. Absorption spectroscopy is employed as an analytical chemistry tool to determine the presence of a particular substance in a sample and, in many cases, to quantify the amount of the substance present. Infrared and ultraviolet–visible spectroscopy are particularly common in analytical applications. Absorption spectroscopy is also employed in studies of molecular and atomic physics, astronomical spectroscopy and remote sensing. There is a wide range of experimental approaches for measuring absorption spectra. The most common arrangement is to direct ...
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Fluorescence Spectroscopy
Fluorescence spectroscopy (also known as fluorimetry or spectrofluorometry) is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores. Devices that measure fluorescence are called fluorometers. Theory Molecules have various states referred to as energy levels. Fluorescence spectroscopy is primarily concerned with electronic and vibrational states. Generally, the species being examined has a ground electronic state (a low energy state) of interest, and an excited electronic state of higher energy. Within each of these elec ...
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Van 't Hoff Equation
The Van 't Hoff equation relates the change in the equilibrium constant, , of a chemical reaction to the change in temperature, ''T'', given the standard enthalpy change, , for the process. It was proposed by Dutch chemist Jacobus Henricus van 't Hoff in 1884 in his book ''Études de Dynamique chimique'' (''Studies in Dynamic Chemistry''). The Van 't Hoff equation has been widely utilized to explore the changes in state functions in a thermodynamic system. The Van 't Hoff plot, which is derived from this equation, is especially effective in estimating the change in enthalpy and entropy of a chemical reaction. Equation Summary and Uses The standard pressure, P^0, is used to define the reference state for the Van 't Hoff equation, which is where denotes natural logarithm, K_ is the thermodynamic equilibrium constant, and is the ideal gas constant. This equation is exact at any one temperature and all pressures, derived from the requirement that the Gibbs free en ...
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Gas Constant
The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per amount of substance, i.e. the pressure–volume product, rather than energy per temperature increment per ''particle''. The constant is also a combination of the constants from Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. It is a physical constant that is featured in many fundamental equations in the physical sciences, such as the ideal gas law, the Arrhenius equation, and the Nernst equation. The gas constant is the constant of proportionality that relates the energy scale in physics to the temperature scale and the scale used for amount of substance. Thus, the value of the gas constant ultimately derives from historical decisions and accidents in the setting of units of energy, temperature and amount of substa ...
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Thermodynamic Temperature
Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic work and heat transfer as defined in thermodynamics, but the kelvin was redefined by international agreement in 2019 in terms of phenomena that are now understood as manifestations of the kinetic energy of free motion of microscopic particles such as atoms, molecules, and electrons. From the thermodynamic viewpoint, for historical reasons, because of how it is defined and measured, this microscopic kinetic definition is regarded as an "empirical" temperature. It was adopted because in practice it can generally be measured more precisely than can Kelvin's thermodynamic temperature. A thermodynamic temperature reading of zero is of particular importance for the third law of thermodynamics. By convention, it is reported on the ''Kelvin scale'' ...
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Exponential Decay
A quantity is subject to exponential decay if it decreases at a rate proportional to its current value. Symbolically, this process can be expressed by the following differential equation, where is the quantity and (lambda) is a positive rate called the exponential decay constant, disintegration constant, rate constant, or transformation constant: :\frac = -\lambda N. The solution to this equation (see derivation below) is: :N(t) = N_0 e^, where is the quantity at time , is the initial quantity, that is, the quantity at time . Measuring rates of decay Mean lifetime If the decaying quantity, ''N''(''t''), is the number of discrete elements in a certain set, it is possible to compute the average length of time that an element remains in the set. This is called the mean lifetime (or simply the lifetime), where the exponential time constant, \tau, relates to the decay rate constant, λ, in the following way: :\tau = \frac. The mean lifetime can be looked at as a ...
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