The Kapustinskii equation calculates the lattice energy UL for an ionic crystal, which is experimentally difficult to determine. It is named after Anatoli Fedorovich Kapustinskii who published the formula in 1956. [1]
where | K = 1.20200×10−4 J·m·mol−1 |
d = 3.45×10−11 m | |
ν is the number of ions in the empirical formula, | |
z+ and z− are the numbers of elementary charge on the cation and anion, respectively, and | |
r+ and r− are the radii of the cation and anion, respectively, in meters. |
The calculated lattice energy gives a good estimation for the Born–Landé equation; the real value differs in most cases by less than 5%.
Furthermore, one is able to determine the ionic radii (or more properly, the thermochemical radius) using the Kapustinskii equation when the lattice energy is known. This is useful for rather complex ions like sulfate (SO2−
4) or phosphate (PO3−
4).
Kapustinskii originally proposed the following simpler form, which he faulted as "associated with antiquated concepts of the character of repulsion forces". [1] [2]
Here, K' = 1.079×10−4 J·m·mol−1. This form of the Kapustinskii equation may be derived as an approximation of the Born–Landé equation, below. [1] [2]
Kapustinskii replaced r0, the measured distance between ions, with the sum of the corresponding ionic radii. In addition, the Born exponent, n, was assumed to have a mean value of 9. Finally, Kapustinskii noted that the Madelung constant, M, was approximately 0.88 times the number of ions in the empirical formula. [2] The derivation of the later form of the Kapustinskii equation followed similar logic, starting from the quantum chemical treatment in which the final term is 1 − d/r0 where d is as defined above. Replacing r0 as before yields the full Kapustinskii equation. [1]
In a chemical reaction, chemical equilibrium is the state in which both the 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. 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 they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium.
In thermodynamics, the specific heat capacity of a substance is the heat capacity of a sample of the substance divided by the mass of the sample, also sometimes referred to as massic heat capacity or as the specific heat. Informally, it is the amount of heat that must be added to one unit of mass of the substance in order to cause an increase of one unit in temperature. The SI unit of specific heat capacity is joule per kelvin per kilogram, J⋅kg−1⋅K−1. For example, the heat required to raise the temperature of 1 kg of water by 1 K is 4184 joules, so the specific heat capacity of water is 4184 J⋅kg−1⋅K−1.
In particle physics, the Dirac equation is a relativistic wave equation derived by British physicist Paul Dirac in 1928. In its free form, or including electromagnetic interactions, it describes all spin-1⁄2 massive particles, called "Dirac particles", such as electrons and quarks for which parity is a symmetry. It is consistent with both the principles of quantum mechanics and the theory of special relativity, and was the first theory to account fully for special relativity in the context of quantum mechanics. It was validated by accounting for the fine structure of the hydrogen spectrum in a completely rigorous way.
The Navier–Stokes equations are partial differential equations which describe the motion of viscous fluid substances, named after French engineer and physicist Claude-Louis Navier and Irish physicist and mathematician George Gabriel Stokes. They were developed over several decades of progressively building the theories, from 1822 (Navier) to 1842-1850 (Stokes).
The Stefan–Boltzmann law, also known as Stefan's law, describes the intensity of the thermal radiation emitted by matter in terms of that matter's temperature. It is named for Josef Stefan, who empirically derived the relationship, and Ludwig Boltzmann who derived the law theoretically.
In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities of the chemical species undergoing reduction and oxidation respectively. It was named after Walther Nernst, a German physical chemist who formulated the equation.
In physics, Hooke's law is an empirical law which states that the force needed to extend or compress a spring by some distance scales linearly with respect to that distance—that is, Fs = kx, where k is a constant factor characteristic of the spring, and x is small compared to the total possible deformation of the spring. The law is named after 17th-century British physicist Robert Hooke. He first stated the law in 1676 as a Latin anagram. He published the solution of his anagram in 1678 as: ut tensio, sic vis. Hooke states in the 1678 work that he was aware of the law since 1660.
In thermodynamics and solid-state physics, the Debye model is a method developed by Peter Debye in 1912 for estimating the phonon contribution to the specific heat in a solid. It treats the vibrations of the atomic lattice (heat) as phonons in a box, in contrast to the Einstein photoelectron model, which treats the solid as many individual, non-interacting quantum harmonic oscillators. The Debye model correctly predicts the low-temperature dependence of the heat capacity of solids, which is proportional to – the Debye T 3 law. Similarly to the Einstein photoelectron model, it recovers the Dulong–Petit law at high temperatures. Due to simplifying assumptions, its accuracy suffers at intermediate temperatures.
In differential geometry, the four-gradient is the four-vector analogue of the gradient from vector calculus.
The Madelung constant is used in determining the electrostatic potential of a single ion in a crystal by approximating the ions by point charges. It is named after Erwin Madelung, a German physicist.
Ionic radius, rion, is the radius of a monatomic ion in an ionic crystal structure. Although neither atoms nor ions have sharp boundaries, they are treated as if they were hard spheres with radii such that the sum of ionic radii of the cation and anion gives the distance between the ions in a crystal lattice. Ionic radii are typically given in units of either picometers (pm) or angstroms (Å), with 1 Å = 100 pm. Typical values range from 31 pm (0.3 Å) to over 200 pm (2 Å).
The chemists Peter Debye and Erich Hückel noticed that solutions that contain ionic solutes do not behave ideally even at very low concentrations. So, while the concentration of the solutes is fundamental to the calculation of the dynamics of a solution, they theorized that an extra factor that they termed gamma is necessary to the calculation of the activities of the solution. Hence they developed the Debye–Hückel equation and Debye–Hückel limiting law. The activity is only proportional to the concentration and is altered by a factor known as the activity coefficient . This factor takes into account the interaction energy of ions in solution.
In chemistry, the lattice energy is the energy change upon formation of one mole of a crystalline ionic compound from its constituent ions, which are assumed to initially be in the gaseous state. It is a measure of the cohesive forces that bind ionic solids. The size of the lattice energy is connected to many other physical properties including solubility, hardness, and volatility. Since it generally cannot be measured directly, the lattice energy is usually deduced from experimental data via the Born–Haber cycle.
In statistical thermodynamics, the UNIFAC method is a semi-empirical system for the prediction of non-electrolyte activity in non-ideal mixtures. UNIFAC uses the functional groups present on the molecules that make up the liquid mixture to calculate activity coefficients. By using interactions for each of the functional groups present on the molecules, as well as some binary interaction coefficients, the activity of each of the solutions can be calculated. This information can be used to obtain information on liquid equilibria, which is useful in many thermodynamic calculations, such as chemical reactor design, and distillation calculations.
The Born–Landé equation is a means of calculating the lattice energy of a crystalline ionic compound. In 1918 Max Born and Alfred Landé proposed that the lattice energy could be derived from the electrostatic potential of the ionic lattice and a repulsive potential energy term.
Diffusion is the net movement of anything generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical potential. It is possible to diffuse "uphill" from a region of lower concentration to a region of higher concentration, as in spinodal decomposition. Diffusion is a stochastic process due to the inherent randomness of the diffusing entity and can be used to model many real-life stochastic scenarios. Therefore, diffusion and the corresponding mathematical models are used in several fields beyond physics, such as statistics, probability theory, information theory, neural networks, finance, and marketing.
The isotopic shift is the shift in various forms of spectroscopy that occurs when one nuclear isotope is replaced by another.
In chemistry, ion transport number, also called the transference number, is the fraction of the total electric current carried in an electrolyte by a given ionic species i:
The Born–Mayer equation is an equation that is used to calculate the lattice energy of a crystalline ionic compound. It is a refinement of the Born–Landé equation by using an improved repulsion term.
The perturbed γ-γ angular correlation, PAC for short or PAC-Spectroscopy, is a method of nuclear solid-state physics with which magnetic and electric fields in crystal structures can be measured. In doing so, electrical field gradients and the Larmor frequency in magnetic fields as well as dynamic effects are determined. With this very sensitive method, which requires only about 10-1000 billion atoms of a radioactive isotope per measurement, material properties in the local structure, phase transitions, magnetism and diffusion can be investigated. The PAC method is related to nuclear magnetic resonance and the Mössbauer effect, but shows no signal attenuation at very high temperatures. Today only the time-differential perturbed angular correlation (TDPAC) is used.