The acid dissociation constant quantifies the chemical equilibrium for loss of one proton from a chemical acid. In water, write the actual proton transfer as . Its full dimensionless equilibrium constant is
The usual aqueous acid dissociation constant uses the solvent convention with water thermodynamic activity approximated by one:
Here hydrated hydrogen ions are understood; is shorthand, not an isolated bare proton in the chemical solution. All thermodynamic activities and are dimensionless quantities, using consistent standard states. If water thermodynamic activity differs appreciably from one, retain it in the full equilibrium constant instead of silently mixing conventions.
With activity coefficients and reference concentration , put for each solute. Then
The last expression is the dilute ideal concentration approximation, not the definition in a nonideal chemical solution. Omitting instead produces a quotient with units of concentration; its numerical value depends on the chosen units. Do not take a logarithm of that dimensional quotient. Conditional concentration quotients can change with ionic strength even at fixed temperature, whereas the thermodynamic acid dissociation constant retains the activity coefficient corrections. The acid dissociation constant entry distinguishes these conventions.
At the same temperature, solvent and standard states, a larger acid dissociation constant, equivalently a smaller pKa, indicates a stronger tendency to donate a proton. It does not specify an analytical concentration, a pH, or a reaction rate. Composition and the weak acid mass and charge balances are needed to predict pH; chemical kinetics addresses how quickly the chemical equilibrium is approached.
Activation energy 2026-10-13
A small increase in temperature can produce a large increase in a reaction rate. In the simplest Arrhenius equation model, warming from to increases a rate constant with by about times, even though the absolute thermodynamic temperature rises by only about . This sensitivity helps explain why cooling can slow unwanted chemical reactions and why a hot process can become difficult to control. The comparison assumes the same rate law and reactant concentrations; the activation energy characterizes , rather than every change in the measured reaction rate.
The physical motivation is the distribution of molecular energies. Warming changes the Boltzmann distribution, increasing the relative population of energetically costly configurations. A transition state can therefore become much more accessible than the modest change in average kinetic energy might suggest. The exponential function in an Arrhenius equation captures such sensitivity in a simple model; it is not a universal formula for the fraction above every barrier in a Maxwell-Boltzmann distribution.[ref]
Activation energy quantifies how strongly a rate constant depends on thermodynamic temperature. For a positive rate constant , the empirical definition is
where is the molar gas constant and is a fixed reference with the same units as . The ratio is a dimensionless quantity, keeping the natural logarithm meaningful without changing its derivative. Thus is a molar energy, commonly in or . The Arrhenius equation makes constant over its assumed range. This rate-based definition, and the need for care when identifying it with a threshold on a potential energy surface, are stated in the activation energy.
In a simple barrier picture, reaching a transition state costs energy relative to the starting reactants. The height of that barrier is different from the difference between the reactants and reaction products. An energetically favourable endpoint can still be reached slowly. An energy profile makes the distinction visible, while an Arrhenius plot tests temperature sensitivity from rate constants. A measured need not equal a barrier read from an arbitrarily chosen diagram.
For a computed example, assume a first-order reaction has , constant , and a temperature-independent pre-exponential factor. The Arrhenius equation gives
Hence . Its half-life falls from to . These are chosen model parameters, not measurements of an identified chemical reaction. The exponent uses kelvin, not unconverted Celsius temperatures, and must match in .
Figure 1.
Synthetic potential-energy profiles: starting levels determine directional reaction energy barriers
. Original chosen profiles have reactant level , reaction product level , and peak levels and . Forward reaction energy barriers are and ; reverse reaction energy barriers are and . The reaction coordinate is not time. These curves are illustrative functions, not laboratory measurements or calculated molecular potential energy surfaces; their heights do not by themselves specify Arrhenius activation energies. Details.
A microscopic reaction energy barrier belongs to a specified path on a potential energy surface. An experimental activation energy belongs to a specified rate constant and its temperature dependence. A multi-step reaction mechanism can change which step controls the observed conversion, and a temperature-dependent pre-exponential factor contributes to the observed activation energy. Even the Gibbs energy of activation of transition state theory is a different quantity: it incorporates entropy as well as enthalpy and depends on the standard states. These distinctions prevent a fitted Arrhenius plot from being mistaken for a direct microscopic energy measurement.[ref]
Catalysis illustrates the separation between a path and its endpoints. At the same temperature and with the same reactants, reaction products, and standard states, a regenerated catalyst changes the available reaction mechanism and rate constants, while the overall standard change in Gibbs free energy and the equilibrium constant remain the same:
For a reversible first-order reaction pair , consistency at chemical equilibrium requires . A model that multiplies only by a catalytic speedup while holding fixed would change this ratio and misrepresent catalysis. This simple ratio applies to that specified rate law; a multi-step catalytic reaction mechanism needs its own rate equations. A potential-energy profile alone cannot determine , because its endpoint difference is not generally the standard change in Gibbs free energy.[ref]
Arrhenius equation 2026-10-13
The Arrhenius equation models the temperature dependence of a rate constant by
Here is the pre-exponential factor, the activation energy, the molar gas constant, and the absolute thermodynamic temperature. In its original form, and are held constant over the range being modeled. It is an empirical relationship, not a universal rule for every reaction mechanism. See the Arrhenius equation.
Eliminating between two positive temperatures gives the useful prediction
For , warming increases . The logarithmic sensitivity is , so there is no universal doubling per ten degrees. The same rise from to gives a factor for , versus for .
Figure 1. . Both models are anchored at , so they have different pre-exponential factors. Left: the higher activation energy produces a larger relative change with temperature. Right: the natural logarithm of the dimensionless ratio is linear in inverse temperature. These exact model curves are not experimental data. Details.
The useful simplification is that a strong change in reaction rate becomes a straight-line relation after changing variables. Measurements at several temperatures can estimate the slope and test whether one pair of constants describes the chosen range. Curvature can indicate a failure of that approximation; fitting a line does not uniquely establish a microscopic reaction mechanism.
Svante Arrhenius's 1889 paper on sucrose conversion through catalysis by a chemical acid compared the strong observed temperature dependence with the much smaller increase in collision frequency. He discussed van't Hoff's earlier temperature relations and proposed a small population of hypothetical active sucrose, replenished from ordinary sucrose, to interpret the dependence. The inspected translated excerpt derives an inverse-temperature relation in its equations (6)–(7) and then applies it to the reaction rate. That historical hypothesis is distinct from a modern transition state description. See the On the Reaction Velocity of the Inversion of Cane Sugar by Acids. The excerpt omits parts of the original paper; it does not provide a complete original apparatus description or dataset.
The pre-exponential factor must have the same units as the rate constant, since the exponential function supplies a dimensionless quantity. For a rate law , both and have units . Thus a first-order reaction uses , whereas a second-order reaction uses . Calling a frequency factor does not give it frequency units for every order of reaction. Its value includes the physical and geometrical factors allowed by the chosen reaction mechanism; equal activation energies need not mean equal reaction rates.
Figure 2. . Both chosen first-order reaction models have and the same exponent parameter . Blue uses a constant pre-exponential factor; orange multiplies it by . All markers are synthetic evaluations, not observations. Left: natural logarithm of against . Right: the corresponding apparent activation energies, and in . The dashed orange tangent at has numerical slope on the displayed horizontal scale. Details.
To read the blue Arrhenius plot, define the dimensionless quantity and . Its numerical slope is , giving . The slope against , by contrast, is . The orange tangent at gives ; its finite-interval slope between and gives about . The distinction between a local derivative and a fitted interval matters even with perfectly noise-free synthetic evaluations.
Two measured positive rate constants give a two-point estimate
Several temperatures let linear regression test the constant-parameter approximation: inspect the regression residuals, keep the same rate law and composition convention, and account for uncertainty in both and . A straight line over a short range supports a useful local approximation; it does not uniquely identify a reaction mechanism. A fixed change of units or of shifts the intercept without changing the inferred activation energy.[ref]
Controllability 2026-10-13
Controllability asks whether the available control inputs can move a dynamical system between every pair of states in its declared state space. Fixing a duration gives the precise condition for every , where is the state space and its reachable set. With freely chosen duration, every pair must instead be connectable in some permitted finite time, which may depend on the pair. Always specify admissible control inputs, deadlines and any constraints along the path. [ref]
The surprising part is that one control input can control several state variables by acting at different times. For the double integrator, acceleration changes velocity directly, while the accumulated velocity changes position. Starting from rest, accelerate during the first half of the journey and brake during the second: the final velocity can vanish although the final position has changed. The figure is an analytic mathematical example in dimensionless quantities, with no experimental measurements.
Figure 1.
Timing one control input controls both position and velocity
. The double integrator starts at and runs to . Left: for one time unit, then for one time unit. Middle: the analytic state path ends at , after reaching when braking begins. Right: unit inputs on the first and second halves separately contribute and to the endpoint. Their linear combinations fill the plane when input amplitudes are unrestricted real numbers; subtracting the second contribution from the first gives . Details.
Controllability is useful before trying to design a controller: a requested endpoint outside the reachable set cannot be attained by clever choice of feedback control. The Kalman rank criterion makes this an exact linear algebra calculation for the stated linear time-invariant system model. It concerns whole states, so attaining one plant output is not enough to establish controllability. In quantum control, the declared state space may be an orbit constrained by conservation laws; see quantum controllability and unitary orbit of a density operator.
Control theory Created 2026-09-24 Updated 2026-10-13
Control theory studies how to choose control inputs for a dynamical system so that its plant output follows a reference signal, despite control disturbances and imperfect knowledge of the controlled plant. A controller turns the available information into a control signal. The design must consider both the resulting response and stability theory: a rule that corrects a small mismatch can still produce growing deviations if the interconnection is badly chosen. [ref]
The central distinction is informational. Open-loop control executes planned commands; feedback control uses the measured output of the actual controlled plant to update those commands. A reference signal can describe a destination, while control disturbances describe influences that the controller did not command. A model can predict where the controlled plant should be; measurement tells the controller what actually happened. The authors provide a free full-book PDF through [ref].
For a concrete comparison, all examples below use the same ideal scalar controlled plant:
Here is an illustrative position, the control input, a control disturbance, and the measured output. Both and are dimensionless quantities; the numbers are chosen to expose the mechanism, with no empirical interpretation. The ordinary differential equation says that the present control input and control disturbance accumulate into . The measured output equals the entire state only in this ideal example; a general plant output need not reveal the entire state.
Figure 1.
Planned commands and feedback control for an ideal controlled plant
. Top: the reference signal and measured output form the tracking error, which the controller converts into a control signal. Bottom left: with no control disturbance, the planned pulse reaches at , while proportional control with feedback gain approaches it smoothly. Bottom right: a control disturbance starts at ; open-loop control drifts, while proportional control approaches . All coordinates are dimensionless quantities. Details.
Covalent bond 2026-10-13
A covalent bond joins chemical atoms through shared Electrons. In the familiar two-centre description, one bond pair contributes to a connection between two atomic nuclei. Sharing means that the Electrons belong to the combined arrangement and interact with both atomic nuclei; it does not mean that identifiable dots shuttle along drawn paths. The [ref] emphasizes the concentration of Electrons between atomic nuclei and the resulting attraction and characteristic separation. The pair picture is especially useful for simple molecules, but is not a universal description of every covalent bond.
A Lewis structure turns this picture into practical bookkeeping. Count the valence electrons, indicate which chemical atoms are connected, and allocate two Electrons to each line. A bond pair is shared; a lone pair is assigned to one chemical atom without connecting it to another. A double line represents two bond pairs. Dots and lines record allocations, rather than positions, trajectories, or a measured three-dimensional arrangement. [ref]
For molecular hydrogen, , each neutral hydrogen chemical atom supplies one valence electron. Thus valence electrons make one bond pair, represented by , with no lone pairs. Each hydrogen counts the same shared pair when checking its two-electron arrangement. The molecule still contains two Electrons, not four: counting a pair around both endpoints does not create extra Electrons.
For water, , neutral oxygen supplies six valence electrons and the two hydrogen chemical atoms supply one each: . Two O–H connections consume four Electrons as two bond pairs. The remaining Electrons form two lone pairs on oxygen. Around oxygen, the two bond pairs and two lone pairs count as eight Electrons; each hydrogen counts two. The whole water molecule has ten Electrons, because two additional oxygen Electrons are omitted from this valence electron drawing.
For ammonia, , the total is valence electrons: five from nitrogen and three from hydrogen. Three N–H connections use six Electrons as three bond pairs, leaving two Electrons as one lone pair on nitrogen. Thus water and ammonia have the same total of eight valence electrons but different allocations: two plus two pairs versus three plus one. This small calculation already distinguishes their connectivity without a detailed quantum mechanics calculation.
Figure 1.
Lewis structures count bond pairs and lone pairs in molecular hydrogen, water, ammonia, and molecular oxygen; schematic layouts do not specify molecular shapes
. Details.
For molecular oxygen, , valence electrons give the conventional Lewis structure. Its two bond pairs use four Electrons, leaving eight as four lone pairs, two on each oxygen. Each oxygen consequently counts eight Electrons locally. However, actual molecular oxygen has two unpaired Electrons and exhibits paramagnetism: it is attracted into a stronger magnetic field. The all-paired Lewis structure cannot capture this observation. Molecular orbital theory describes the unpaired Electrons; the successful counting diagram alone is insufficient. [ref]
Why does sharing produce a stable separation? For molecular hydrogen, the electronic arrangement responds as the atomic nuclei approach. Their interactions can lower the energy, but pushing them too close raises it. A curve of potential energy against separation therefore has a local minimum, rather than falling forever. Attraction and repulsion balance there. This is a statement about the combined system, not a claim that stationary Electrons sit between otherwise motionless atomic nuclei. [ref]
The following Morse potential makes those features calculable. Set , where is separation and its equilibrium value, and let be the well depth. With the self-chosen parameter , define the dimensionless quantities
Here is the net separating force, obtained from the derivative of the potential energy. Positive pushes the chemical atoms apart; negative draws them together. These are illustrative curves with in chosen units, not measured molecular hydrogen data or fitted parameters.
Figure 2.
Illustrative dimensionless Morse potential and its force: a stable local minimum, short-distance repulsion, and separation toward zero potential energy
. Details.
At , and . The second derivative is , confirming a local minimum. At , ; at , . As increases without bound, approaches zero from below. Thus moving from the well bottom to separated chemical atoms requires an increase of in this model's potential energy. An actual quantum mechanics dissociation threshold also depends on the initial motion of the atomic nuclei, so the well depth alone is not every measured dissociation energy.
The force panel separates into a positive term and a negative term . At they are and , cancelling exactly; nearer separations favour the positive term. These are algebraic components of the chosen Morse potential, not separately measured microscopic forces. Their usefulness is to show how a balance arises from the slope of one energy curve.
The beauty of the pair picture is its economy: a few marks summarize connectivity and constrain what a proposed molecule can contain. Its historical anchor is Gilbert N. Lewis's 1916 paper [ref], also available as an [ref]. Lewis structures remain useful because they answer counting questions quickly; quantum mechanics supplies the richer account when energy, shape, or unpaired Electrons matter.
Focal ratio 2026-10-06
The focal ratio is the focal length divided by the entrance aperture diameter. It controls the cone angle of a paraxial focused beam.
Integrating the Maxwell-Boltzmann velocity distribution over directions gives
Normal distribution Created 2026-09-24 Updated 2026-10-06
The normal distribution has density proportional to .
Permittivity Created 2026-10-05 Updated 2026-10-13
Permittivity describes how an electric field and a material's electric polarization combine into the electric displacement field. In a static, local response with linearity and isotropy, and no electric polarization at zero electric field, the constitutive equation is
Here is vacuum permittivity, while is the relative permittivity, a dimensionless quantity. The SI unit of permittivity is farad per metre, : multiplying it by an electric field in gives an electric displacement field in . A larger positive permittivity lets the same parallel-plate capacitor hold more plate electric charge at the same electric potential difference.
The material contribution is electric polarization , the electric dipole moment per unit volume. The electric displacement field and electric susceptibility satisfy
Substitution gives the first constitutive equation. The electric field here is the averaged, total field inside the material, not just the field of the external plate electric charges. The continuum approximation averages over many chemical atoms or molecules; locality means that the electric polarization at a position depends on the electric field there. Static equilibrium, fixed material conditions and sufficiently small electric fields are needed for this scalar proportionality. [ref].
For an ideal parallel-plate capacitor completely filled by a uniform dielectric, hold the free plate electric charge magnitude fixed and neglect the fringing field of a capacitor. Writing for the plate area, Gauss's law gives . Thus
The electric dipoles point along the electric field. Their surface electric charges, described by polarization density, oppose the field from the free plate electric charges. For a hypothetical dielectric with , the internal electric field is one quarter of its vacuum value, while . At fixed electric potential difference instead, the internal electric field stays approximately and the plate electric charge grows fourfold. These are different experimental constraints. [ref].
Figure 1. . An original schematic and normalized model comparison for a uniform dielectric with relative permittivity four. The arrows for electric dipole moments run from negative to positive electric charge; the two field contributions oppose each other. The bar values compare electric displacement field , , and electric polarization , which all have units . The schematic is not to microscopic scale. Details.
Permittivity is a useful material summary, not a universal constant of the material under every condition. Temperature, frequency and electric field strength can change the response. In a linear anisotropic dielectric, permittivity is a tensor, , so the electric displacement field need not be parallel to the electric field. At nonzero frequency, delayed electric polarization requires complex permittivity and may produce dielectric loss. [ref].
pH 2026-10-13
The pH of a chemical solution is the negative base-ten logarithm of its hydrogen ion thermodynamic activity:
The thermodynamic activity is a dimensionless quantity, so the logarithm has a dimensionless argument. The definition uses thermodynamic activity, rather than total chemical acid concentration. Single-ion thermodynamic activities require a convention; practical pH measurements are tied to calibrated standards. See IUPAC Gold Book, pH.
In a dilute ideal chemical solution in water, a useful approximation is
Square brackets denote concentration in moles per litre. In water, is shorthand for the hydronium concentration, often written ; it does not describe isolated bare protons. Departures from ideal behavior need activity coefficients. The concentration formula approximates the thermodynamic activity definition.
For an ideal strong acid supplying one proton per initial unit, stipulate a total concentration of and negligible self-ionization of water. Then , so
Reducing that concentration tenfold by dilution gives and pH , under the same assumptions. More generally, dividing the hydrogen ion thermodynamic activity by ten raises pH by one. This is why the scale compresses an enormous range: equal steps of pH represent multiplicative changes, rather than equal differences in concentration. These are model calculations, rather than measured samples.
Figure 1.
One step of pH represents a tenfold change in hydrogen ion thermodynamic activity
. The logarithm makes equal spacing on the pH axis correspond to factors of ten on the thermodynamic activity axis. The marked strong acid example uses the dilute ideal concentration approximation and negligible self-ionization of water. The plotted interval is illustrative; it does not bound possible pH values. Details.
Neutrality depends on temperature. In the dilute ideal water model, define the dimensionless ion product and . Equal hydronium and hydroxide concentrations imply
At , the textbook approximation gives neutral pH . Since varies with temperature, neutrality need not mean pH . Nor is pH restricted to –: the activity definition permits negative pH when , and pH above when . High concentrations can invalidate the dilute ideal approximation. See Flowers et al., Chemistry 2e, pH and pOH.
S. P. L. Sørensen introduced pH at the Carlsberg Laboratory in 1909, as recorded in the Carlsberg Foundation historical timeline.
Power law Created 2026-09-24 Updated 2026-10-13
A power law is a relation , with fixed constants and . For positive , any real number is allowed. Its useful feature is a simple scaling rule:
The same proportional change of input produces the same proportional change of output, independently of the starting value. The exponent controls that response; the coefficient fixes the magnitude.
For example, the area of a circle is . Doubling the radius multiplies its area by four, and tripling it multiplies the area by nine. The volume of a sphere is : the same changes multiply its volume by eight and twenty-seven. The distinction explains why similarly shaped objects do not preserve their ratio of surface area to volume when their size changes.
When the output is positive, a logarithm turns the power law into a straight-line relation. Using positive reference values and ,
These ratios are dimensionless quantities, so the formula also applies to physical measurements with units. Plotting both ratios on a logarithmic scale gives a line of slope . Changing a unit changes the numerical coefficient, while the exponent stays the same. Positive describes increasing values; negative describes decreasing values; gives a constant. The zero coefficient is a degenerate case with no useful logarithmic slope.
Exact scaling is stronger than regular variation. The function has a doubling ratio tending to four, but its logarithmic correction keeps growing. The diagram contrasts it with the exact power law .
Figure 1.
Exact quadratic scaling and a logarithmic correction have different finite doubling ratios, even though the correction leaves the limiting exponent unchanged
. Details.
A power law for a probability density and a power law for a tail probability have different exponents. For a Pareto distribution with and lower endpoint one,
The tail probability has exponent ; differentiating it and changing sign gives the probability density exponent . Confusing them changes the interpretation of a fitted exponent. The normalizing coefficient and lower endpoint also matter: a decreasing power law is not automatically a valid probability density over the entire positive real line.
The appearance of a line over a finite logarithmic range is evidence to investigate, rather than a proof of an exact power law or its mechanism. In their study of power-law distributions, Clauset, Shalizi and Newman combine maximum likelihood estimation, goodness-of-fit tests and comparisons with alternative models; their abstract explains why ordinary least-squares fitting can give misleading results for tail data. See Aaron Clauset, Cosma Rohilla Shalizi and M. E. J. Newman, Power-law distributions in empirical data, SIAM Review 51 (2009), 661–703. The scaling rule is mathematically exact when it defines a model; whether a dataset supports that model is a question of statistical inference.
Random walk 2026-09-24
A random walk is a stochastic process formed by successive random steps.
Reynolds number Created 2026-09-24 Updated 2026-09-28
The Reynolds number compares inertial and viscous effects.
Scale factor (cosmology) 2026-10-13
The scale factor measures how spatial lengths in an FLRW metric change with cosmic time . Choose to be a dimensionless quantity with at a reference epoch, usually today. For two comoving observers, their fixed radial comoving distance and their proper distance in cosmology satisfy
The proper distance in cosmology is measured along a spatial slice at one cosmic time; it is not the distance that a travelling photon covers between emission and reception. Only ratios of the scale factor have a normalization-independent meaning: replacing by and by leaves unchanged.
For example, take , where means a million parsecs. At , the same pair of comoving observers has proper distance in cosmology respectively. Every such separation changes by the same factor, although more distant pairs gain more distance. The illustration treats the marked objects as ideal comoving observers; internal motions in galaxies need not follow this background scaling.
Figure 1.
The same comoving coordinates at three values of the scale factor, and the Hubble flow recentered on two comoving observers
. The top row keeps the same marked comoving observers and the same plotting scale: adjacent values of proper distance in cosmology are arbitrary length units. The bottom row shows equal local patches of an extended ideal grid at ; arrows represent the Hubble flow relative to each marked comoving observer. The drawn grid is a schematic, not a model of the arrangement of galaxies. Details.
The beauty of the scale factor is that one function describes the changing spatial ruler for every comoving observer. Spatial homogeneity gives no preferred centre of cosmic expansion: in a flat spatial patch, relative positions obey , so recentering on any comoving observer preserves Hubble's law. The evolution of the scale factor is determined by the Friedmann equations, while its ratio between emission and reception determines cosmological redshift.