Standard state
Encyclopedia
In chemistry
, the standard state of a material (pure substance
, mixture or solution
) is a reference point used to calculate its properties under different conditions. In principle, the choice of standard state is arbitrary, although the International Union of Pure and Applied Chemistry
(IUPAC) recommends a conventional set of standard states for general use. IUPAC recommends using a standard pressure po = 1 bar
(100 kilopascals). Strictly speaking, temperature is not part of the definition of a standard state. For example, as discussed below the standard state of a gas is conventionally chosen to be unit pressure (usually in bar) ideal gas
, regardless of the temperature. However, most tables of thermodynamic quantities are compiled at specific temperatures, most commonly 298.15 K (exactly 25 °C) or, somewhat less commonly, 273.15 K (exactly 0 °C). The standard state should not be confused with standard temperature and pressure (STP) for gases, nor with the standard solution
s used in analytical chemistry
.
In the time of their development in the nineteenth century, the superscript plimsoll symbol was adopted to indicate the non-zero nature of the standard state. IUPAC recommends in the 3rd edition of Quantities, Units and Symbols in Physical Chemistry a symbol which seems to be a degree sign (°) as a substitute for the plimsoll mark. In the very same publication the plimsoll mark appears to be constructed by combining a horizontal stroke with a degree sign. A range of similar symbols are used in the literature: a stroked lowercase letter O (o), a superscript zero (0) or a circle with a horizontal bar either where the bar extends the boundaries of the circle (⦵ (Unicode 29B5 "Circle with horizontal bar")) or is enclosed by the circle, dividing the circle in half (⊖ (Unicode 2296 "Circled minus" as displayed in http://www.unicode.org/charts/PDF/U2980.pdf). When compared to the plimsoll symbol used on vessels, the horizontal bar should however extend the boundaries of the circle.
For a given material or substance, the standard state is the reference state for the material's thermodynamic state properties such as enthalpy
, entropy
, Gibbs free energy
, and for many other material standards. The standard enthalpy change of formation
for an element in its standard state is zero, and this convention allows a wide range of other thermodynamic quantities to be calculated and tabulated. The standard state of a substance does not have to exist in nature: for example, it is possible to calculate values for steam
at 25 °C and 1 bar, even though steam does not exist (as a gas) under these conditions. The advantage of this practice is that tables of thermodynamic properties prepared in this way are self-consistent.
o = 0 is defined for the most stable allotrope of the element, such as graphite
in the case of carbon, and the β-phase (white tin) in the case of tin
.
Chemistry
Chemistry is the science of matter, especially its chemical reactions, but also its composition, structure and properties. Chemistry is concerned with atoms and their interactions with other atoms, and particularly with the properties of chemical bonds....
, the standard state of a material (pure substance
Chemical substance
In chemistry, a chemical substance is a form of matter that has constant chemical composition and characteristic properties. It cannot be separated into components by physical separation methods, i.e. without breaking chemical bonds. They can be solids, liquids or gases.Chemical substances are...
, mixture or solution
Solution
In chemistry, a solution is a homogeneous mixture composed of only one phase. In such a mixture, a solute is dissolved in another substance, known as a solvent. The solvent does the dissolving.- Types of solutions :...
) is a reference point used to calculate its properties under different conditions. In principle, the choice of standard state is arbitrary, although the International Union of Pure and Applied Chemistry
International Union of Pure and Applied Chemistry
The International Union of Pure and Applied Chemistry is an international federation of National Adhering Organizations that represents chemists in individual countries. It is a member of the International Council for Science . The international headquarters of IUPAC is located in Zürich,...
(IUPAC) recommends a conventional set of standard states for general use. IUPAC recommends using a standard pressure p
Bar (unit)
The bar is a unit of pressure equal to 100 kilopascals, and roughly equal to the atmospheric pressure on Earth at sea level. Other units derived from the bar are the megabar , kilobar , decibar , centibar , and millibar...
(100 kilopascals). Strictly speaking, temperature is not part of the definition of a standard state. For example, as discussed below the standard state of a gas is conventionally chosen to be unit pressure (usually in bar) ideal gas
Ideal gas
An ideal gas is a theoretical gas composed of a set of randomly-moving, non-interacting point particles. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics.At normal conditions such as...
, regardless of the temperature. However, most tables of thermodynamic quantities are compiled at specific temperatures, most commonly 298.15 K (exactly 25 °C) or, somewhat less commonly, 273.15 K (exactly 0 °C). The standard state should not be confused with standard temperature and pressure (STP) for gases, nor with the standard solution
Standard solution
In analytical chemistry, a standard solution is a solution containing a precisely known concentration of an element or a substance i.e, a known weight of solute is dissolved to make a specific volume. It is prepared using a standard substance, such as a primary standard. Standard solutions are used...
s used in analytical chemistry
Analytical chemistry
Analytical chemistry is the study of the separation, identification, and quantification of the chemical components of natural and artificial materials. Qualitative analysis gives an indication of the identity of the chemical species in the sample and quantitative analysis determines the amount of...
.
In the time of their development in the nineteenth century, the superscript plimsoll symbol was adopted to indicate the non-zero nature of the standard state. IUPAC recommends in the 3rd edition of Quantities, Units and Symbols in Physical Chemistry a symbol which seems to be a degree sign (°) as a substitute for the plimsoll mark. In the very same publication the plimsoll mark appears to be constructed by combining a horizontal stroke with a degree sign. A range of similar symbols are used in the literature: a stroked lowercase letter O (
For a given material or substance, the standard state is the reference state for the material's thermodynamic state properties such as enthalpy
Enthalpy
Enthalpy is a measure of the total energy of a thermodynamic system. It includes the internal energy, which is the energy required to create a system, and the amount of energy required to make room for it by displacing its environment and establishing its volume and pressure.Enthalpy is a...
, entropy
Entropy
Entropy is a thermodynamic property that can be used to determine the energy available for useful work in a thermodynamic process, such as in energy conversion devices, engines, or machines. Such devices can only be driven by convertible energy, and have a theoretical maximum efficiency when...
, Gibbs free energy
Gibbs free energy
In thermodynamics, the Gibbs free energy is a thermodynamic potential that measures the "useful" or process-initiating work obtainable from a thermodynamic system at a constant temperature and pressure...
, and for many other material standards. The standard enthalpy change of formation
Standard enthalpy change of formation
The standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy that accompanies the formation of 1 mole of a substance in its standard state from its constituent elements in their standard states...
for an element in its standard state is zero, and this convention allows a wide range of other thermodynamic quantities to be calculated and tabulated. The standard state of a substance does not have to exist in nature: for example, it is possible to calculate values for steam
Steam
Steam is the technical term for water vapor, the gaseous phase of water, which is formed when water boils. In common language it is often used to refer to the visible mist of water droplets formed as this water vapor condenses in the presence of cooler air...
at 25 °C and 1 bar, even though steam does not exist (as a gas) under these conditions. The advantage of this practice is that tables of thermodynamic properties prepared in this way are self-consistent.
Conventional standard states
Many standard states are non-physical states, often referred to as "hypothetical states". Nevertheless, their thermodynamic properties are well-defined, usually by an extrapolation from some limiting condition, such as zero pressure or zero concentration, to a specified condition (usually unit concentration or pressure) using an ideal extrapolating function, such as ideal solution or ideal gas behavior, or by empirical measurements.Gases
The standard state for a gas is the hypothetical state it would have as a pure substance obeying the ideal gas equation at 1 bar. No real gas has perfectly ideal behaviour, but this definition of the standard state allows corrections for non-ideality to be made consistently for all the different gases.Liquids and solids
The standard state for liquids and solids is simply the state of the pure substance subjected to a total pressure of 1 bar. For elements, the reference point of ΔHfGraphite
The mineral graphite is one of the allotropes of carbon. It was named by Abraham Gottlob Werner in 1789 from the Ancient Greek γράφω , "to draw/write", for its use in pencils, where it is commonly called lead . Unlike diamond , graphite is an electrical conductor, a semimetal...
in the case of carbon, and the β-phase (white tin) in the case of tin
Tin
Tin is a chemical element with the symbol Sn and atomic number 50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group 14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4...
.