Dissociation in
chemistry
Chemistry is the science, scientific study of the properties and behavior of matter. It is a natural science that covers the Chemical element, elements that make up matter to the chemical compound, compounds made of atoms, molecules and ions ...
is a general process in which molecules (or ionic compounds such as
salts
In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively cha ...
, or
complexes) separate or split into other things such as atoms, ions, or
radicals, usually in a reversible manner. For instance, when an
acid
In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
dissolves in water, a
covalent bond
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
between an
electronegative
Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...
atom and a hydrogen atom is broken by
heterolytic fission
In chemistry, heterolysis or heterolytic fission () is the process of cleaving/breaking a covalent bond where one previously bonded species takes both original bonding electrons from the other species. During heterolytic bond cleavage of a neutra ...
, which gives a proton (H
+) and a negative
ion
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
. Dissociation is the opposite of association or recombination.
Dissociation constant
For reversible dissociations in a
chemical equilibrium
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 sy ...
:
AB <=> A + B
the
dissociation constant
In chemistry, biochemistry, and pharmacology, a dissociation constant (K_D) is a specific type of equilibrium constant that measures the propensity of a larger object to separate (dissociate) reversibly into smaller components, as when a complex fa ...
''K''
d is the ratio of dissociated to undissociated compound
:
where the brackets denote the equilibrium concentrations of the species.
[
]
Dissociation degree
The dissociation degree is the fraction of original solute molecules that have dissociated. It is usually indicated by the Greek symbol α. More accurately, degree of dissociation refers to the amount of solute dissociated into ions or radicals per mole. In case of very strong acids and bases, degree of dissociation will be close to 1. Less powerful acids and bases will have lesser degree of dissociation. There is a simple relationship between this parameter and the van 't Hoff factor
The van 't Hoff factor (named after Dutch chemist Jacobus Henricus van 't Hoff) is a measure of the effect of a solute on colligative properties such as osmotic pressure, relative lowering in vapor pressure, boiling-point elevation and freez ...
. If the solute substance dissociates into ions, then
:
For instance, for the following dissociation
:KCl <=> K+ + Cl-
As , we would have that .
Salts
The dissociation of salts by solvation
Solvation (or dissolution) describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the ...
in a solution
Solution may refer to:
* Solution (chemistry), a mixture where one substance is dissolved in another
* Solution (equation), in mathematics
** Numerical solution, in numerical analysis, approximate solutions within specified error bounds
* Soluti ...
, such as water
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
, means the separation of the anion
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s and cation
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
s. The salt can be recovered by evaporation
Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. High concentration of the evaporating substance in the surrounding gas significantly slows down evaporation, such as when humidi ...
of the solvent.
An ''electrolyte
An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electrons. This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Upon dis ...
'' refers to a substance that contains free ions and can be used as an electrically conductive
Electrical resistivity (also called specific electrical resistance or volume resistivity) is a fundamental property of a material that measures how strongly it resists electric current. A low resistivity indicates a material that readily allows ...
medium. Most of the solute does not dissociate in a weak electrolyte, whereas in a strong electrolyte a higher ratio of solute dissociates to form free ions.
A weak electrolyte is a substance whose solute exists in solution mostly in the form of molecules (which are said to be "undissociated"), with only a small fraction in the form of ions. Simply because a substance does not readily dissolve does not make it a weak electrolyte. Acetic acid
Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...
() and ammonium
The ammonium cation is a positively-charged polyatomic ion with the chemical formula or . It is formed by the protonation of ammonia (). Ammonium is also a general name for positively charged or protonated substituted amines and quaternary a ...
() are good examples. Acetic acid is extremely soluble in water, but most of the compound dissolves into molecules, rendering it a weak electrolyte. Weak bases and weak acids are generally weak electrolytes. In an aqueous solution there will be some and some and .
A strong electrolyte is a solute that exists in solution completely or nearly completely as ions. Again, the strength of an electrolyte is defined as the percentage of solute that is ions, rather than molecules. The higher the percentage, the stronger the electrolyte. Thus, even if a substance is not very soluble, but does dissociate completely into ions, the substance is defined as a strong electrolyte. Similar logic applies to a weak electrolyte. Strong acids and bases are good examples, such as HCl and . These will all exist as ions in an aqueous medium.
Gases
The degree of dissociation in gas
Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma).
A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
es is denoted by the symbol , where refers to the percentage of gas molecules which dissociate. Various relationships between and exist depending on the stoichiometry
Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions.
Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equal ...
of the equation. The example of dinitrogen tetroxide
Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium ...
() dissociating to nitrogen dioxide
Nitrogen dioxide is a chemical compound with the formula . It is one of several nitrogen oxides. is an intermediate in the industrial synthesis of nitric acid, millions of tons of which are produced each year for use primarily in the producti ...
() will be taken.
:N2O4 <=> 2NO2
If the initial concentration of dinitrogen tetroxide is 1 mole
Mole (or Molé) may refer to:
Animals
* Mole (animal) or "true mole", mammals in the family Talpidae, found in Eurasia and North America
* Golden moles, southern African mammals in the family Chrysochloridae, similar to but unrelated to Talpida ...
per litre
The litre (international spelling) or liter (American English spelling) (SI symbols L and l, other symbol used: ℓ) is a metric unit of volume. It is equal to 1 cubic decimetre (dm3), 1000 cubic centimetres (cm3) or 0.001 cubic metre (m3). ...
, this will decrease by at equilibrium giving, by stoichiometry, moles of . The 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 ...
(in terms of pressure) is given by the equation
:
where represents the partial pressure
In 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 ...
. Hence, through the definition of partial pressure and using to represent the total pressure and to represent the mole fraction;
:
The total number of moles at equilibrium is which is equivalent to Thus, substituting the mole fractions with actual values in term of and simplifying;
:
This equation is in accordance with Le Chatelier's Principle
Le Chatelier's principle (pronounced or ), 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 c ...
. will remain constant with temperature. The addition of pressure to the system will increase the value of so must decrease to keep constant. In fact, increasing the pressure of the equilibrium favours a shift to the left favouring the formation of dinitrogen tetroxide (as on this side of the equilibrium there is less pressure since pressure is proportional to number of moles) hence decreasing the extent of dissociation
Acids in aqueous solution
The reaction of an acid in water solvent is often described as a dissociation
:HA <=> H+ + A-
where HA is a proton acid such as acetic acid, CH3COOH. The double arrow means that this is an equilibrium process, with dissociation and recombination occurring at the same time. This implies that the acid dissociation constant
In chemistry, an acid dissociation constant (also known as acidity constant, or acid-ionization constant; denoted ) is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction
:HA ...
:
However a more accurate description is provided by the Brønsted–Lowry acid–base theory
The Brønsted–Lowry theory (also called proton theory of acids and bases) is an acid–base reaction theory which was proposed independently by Johannes Nicolaus Brønsted and Thomas Martin Lowry in 1923. The fundamental concept of this theory ...
, which specifies that the ''proton'' H+ does not exist as such in solution but is instead ''accepted'' by (bonded to) a water molecule to form the hydronium
In chemistry, hydronium (hydroxonium in traditional British English) is the common name for the aqueous cation , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is d ...
ion H3O+.
The reaction is therefore more correctly written as
:HA + H2O <=> H3O+ + A-
and better described as an ''ionization'' or formation of ions (for the case when HA has no net charge). The equilibrium constant is then
:
where _2O
2O or 2-O may refer to:
*2o Sector, see Secondary sector of the economy
*2'-O-methylation
*2O, IATA code for Island Air Service in Alaska; see Essential Air Service
See also
*2OOO, a Sydney, Australia radio station
*O2 (disambiguation)
*H2O, ...
/chem> is not included because in dilute solution the solvent is essentially a pure liquid with a thermodynamic activity
In chemical thermodynamics, activity (symbol ) is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depen ...
of one.
Ka is variously named a ''dissociation constant'',[ Laidler K.J. ''Physical Chemistry with Biological Applications'' (Benjamin/Cummings) 1978, p.307 ] an ''acid ionization constant'', an ''acidity constant''[Atkins P. and de Paula J. ''Physical Chemistry'' (8th ed. W.H.Freeman 2006) p.763 ] or an ''ionization constant''. It serves as an indicator of the acid strength: stronger acids have a higher ''K''a value (and a lower p''K''a value).
Fragmentation
Fragmentation of a molecule can take place by a process of heterolysis or homolysis.
Receptors
Receptors
Receptor may refer to:
*Sensory receptor, in physiology, any structure which, on receiving environmental stimuli, produces an informative nerve impulse
*Receptor (biochemistry), in biochemistry, a protein molecule that receives and responds to a n ...
are protein
Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residues. Proteins perform a vast array of functions within organisms, including catalysing metabolic reactions, DNA replication, respo ...
s that bind small ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electr ...
s. The dissociation constant ''K''d is used as indicator of the affinity
Affinity may refer to:
Commerce, finance and law
* Affinity (law), kinship by marriage
* Affinity analysis, a market research and business management technique
* Affinity Credit Union, a Saskatchewan-based credit union
* Affinity Equity Par ...
of the ligand to the receptor. The higher the affinity of the ligand for the receptor the lower the ''K''d value (and the higher the p''K''d value).
See also
*Bond-dissociation energy
The bond-dissociation energy (BDE, ''D''0, or ''DH°'') is one measure of the strength of a chemical bond . It can be defined as the standard enthalpy change when is cleaved by homolysis to give fragments A and B, which are usually radical s ...
*Photodissociation
Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule. ...
, dissociation of molecules by photons (light, gamma rays, x-rays)
*Radiolysis
Radiolysis is the dissociation of molecules by ionizing radiation. It is the cleavage of one or several chemical bonds resulting from exposure to high-energy flux. The radiation in this context is associated with ionizing radiation; radiolysis is ...
, dissociation of molecules by ionizing radiation
*Thermal decomposition
Thermal decomposition, or thermolysis, is a chemical decomposition caused by heat. The decomposition temperature of a substance is the temperature at which the substance chemically decomposes. The reaction is usually endothermic as heat is req ...
References
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Chemical processes
Equilibrium chemistry