In chemistry, the law of definite proportions, sometimes called Proust's law, or law of constant composition states that a given

chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...

always contains its component elements in fixed ratio (by mass) and does not depend on its source and method of preparation. For example,

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as ...

makes up about ⁸/₉ of the mass of any sample of pure

water Water (chemical formula ) is an Inorganic compound, inorganic, transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living ...

, while

hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...

makes up the remaining ¹/₉ of the mass: the mass of two elements in a compound are always in the same ratio. Along with the

law of multiple proportions In chemistry, the law of multiple proportions states that if two elements form more than one compound, then the ratios of the masses of the second element which combine with a fixed mass of the first element will always be ratios of small whole ...

, the law of definite proportions forms the basis of stoichiometry.

History

The law of constant proportion was given by

Joseph Proust Joseph Louis Proust (26 September 1754 – 5 July 1826) was a French chemist. He was best known for his discovery of the law of definite proportions in 1794, stating that chemical compounds always combine in constant proportions. Life Joseph L. ...

in 1797. This observation was first made by the

English English usually refers to: * English language * English people English may also refer to: Peoples, culture, and language * ''English'', an adjective for something of, from, or related to England ** English national ide ...

theologian and chemist

Joseph Priestley Joseph Priestley (; 24 March 1733 – 6 February 1804) was an English chemist, natural philosopher, separatist theologian, grammarian, multi-subject educator, and liberal political theorist. He published over 150 works, and conducted exp ...

, and

Antoine Lavoisier Antoine-Laurent de Lavoisier ( , ; ; 26 August 17438 May 1794),
CNRS (

Claude Louis Berthollet Claude Louis Berthollet (, 9 December 1748 – 6 November 1822) was a Savoyard-French chemist who became vice president of the French Senate in 1804. He is known for his scientific contributions to theory of chemical equilibria via the mecha ...

, who argued that the elements could combine in any proportion. The existence of this debate demonstrates that, at the time, the distinction between pure

s and mixtures had not yet been fully developed. The law of definite proportions contributed to, and was placed on a firm theoretical basis by, the

atomic theory Atomic theory is the scientific theory that matter is composed of particles called atoms. Atomic theory traces its origins to an ancient philosophical tradition known as atomism. According to this idea, if one were to take a lump of matter ...

that John Dalton promoted beginning in 1803, which explained matter as consisting of discrete

atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, ...

s, that there was one type of atom for each element, and that the compounds were made of combinations of different types of atoms in fixed proportions.Dalton, J. (1808). ''A New System of Chemical Philosophy, volume 1'', Manchester
Excerpt
. Accessed 2008-05-08. A related early idea was

Prout's hypothesis Prout's hypothesis was an early 19th-century attempt to explain the existence of the various chemical elements through a hypothesis regarding the internal structure of the atom. In 1815 and 1816, the English chemist William Prout published two p ...

, formulated by English chemist

William Prout William Prout FRS (; 15 January 1785 – 9 April 1850) was an English chemist, physician, and natural theologian. He is remembered today mainly for what is called Prout's hypothesis. Biography Prout was born in Horton, Gloucestershire in ...

, who proposed that the hydrogen atom was the fundamental atomic unit. From this hypothesis was derived the

whole number rule In chemistry, the whole number rule states that the masses of the isotopes are whole number multiples of the mass of the hydrogen atom. The rule is a modified version of Prout's hypothesis proposed in 1815, to the effect that atomic weights are mu ...

, which was the rule of thumb that atomic masses were whole number multiples of the mass of hydrogen. This was later rejected in the 1820s and 30s following more refined measurements of atomic mass, notably by Jöns Jacob Berzelius, which revealed in particular that the atomic mass of

chlorine Chlorine is a chemical element with the symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine i ...

was 35.45, which was incompatible with the hypothesis. Since the 1920s this discrepancy has been explained by the presence of isotopes; the atomic mass of any isotope is very close to satisfying the whole number rule, with the mass defect caused by differing

binding energies In physics and chemistry, binding energy is the smallest amount of energy required to remove a particle from a system of particles or to disassemble a system of particles into individual parts. In the former meaning the term is predominantly use ...

being significantly smaller.

Non-stoichiometric compounds/Isotopes

Although very useful in the foundation of modern chemistry, the law of definite proportions is not universally true. There exist

non-stoichiometric compound In chemistry, non-stoichiometric compounds are chemical compounds, almost always solid inorganic compounds, having elemental composition whose proportions cannot be represented by a ratio of small natural numbers (i.e. an empirical formula); m ...

s whose elemental composition can vary from sample to sample. Such compounds follow the law of multiple proportion. An example is the iron oxide

wüstite Wüstite ( Fe O) is a mineral form of iron(II) oxide found with meteorites and native iron. It has a grey colour with a greenish tint in reflected light. Wüstite crystallizes in the isometric-hexoctahedral crystal system in opaque to translu ...

, which can contain between 0.83 and 0.95 iron atoms for every oxygen atom, and thus contain anywhere between 23% and 25% oxygen by mass. The ideal formula is FeO, but due to crystallographic vacancies it is about Fe_0.95O. In general, Proust's measurements were not precise enough to detect such variations. In addition, the isotopic composition of an element can vary depending on its source, hence its contribution to the mass of even a pure stoichiometric compound may vary. This variation is used in

radiometric dating Radiometric dating, radioactive dating or radioisotope dating is a technique which is used to date materials such as rocks or carbon, in which trace radioactive impurities were selectively incorporated when they were formed. The method compares ...

since

astronomical Astronomy () is a natural science that studies celestial objects and phenomena. It uses mathematics, physics, and chemistry in order to explain their origin and evolution. Objects of interest include planets, moons, stars, nebulae, galaxi ...

, atmospheric,

ocean The ocean (also the sea or the world ocean) is the body of salt water that covers approximately 70.8% of the surface of Earth and contains 97% of Earth's water. An ocean can also refer to any of the large bodies of water into which the wo ...

ic, crustal and deep

Earth Earth is the third planet from the Sun and the only astronomical object known to harbor life. While large volumes of water can be found throughout the Solar System, only Earth sustains liquid surface water. About 71% of Earth's surfa ...

processes may concentrate some

environmental isotopes The environmental isotopes are a subset of isotopes, both stable and radioactive, which are the object of isotope geochemistry. They are primarily used as tracers to see how things move around within the ocean-atmosphere system, within terrestrial b ...

preferentially. With the exception of

and its isotopes, the effect is usually small, but is measurable with modern-day instrumentation. Many natural

polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...

s vary in composition (for instance DNA,

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, res ...

carbohydrate In organic chemistry, a carbohydrate () is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms, usually with a hydrogen–oxygen atom ratio of 2:1 (as in water) and thus with the empirical formula (where ''m'' may or m ...

s) even when "pure". Polymers are generally not considered "pure chemical compounds" except when their molecular weight is uniform (mono-disperse) and their stoichiometry is constant. In this unusual case, they still may violate the law due to isotopic variations.

References

{{reflist Amount of substance Stoichiometry Chemical formulas