Law of definite proportions

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In chemistry, the law of definite proportions, sometimes called Proust's law or the law of constant composition, states that a given chemical compound always contains its component elements in a fixed ratio (by mass) and does not depend on its source or method of preparation. For example, oxygen makes up about 8/9 of the mass of any sample of pure water, while hydrogen 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, the law of definite proportions forms the basis of stoichiometry. [1]

Contents

History

The law of definite proportion was given by Joseph Proust in 1797. [2]

I shall conclude by deducing from these experiments the principle I have established at the commencement of this memoir, viz. that iron like many other metals is subject to the law of nature which presides at every true combination, that is to say, that it unites with two constant proportions of oxygen. In this respect it does not differ from tin, mercury, and lead, and, in a word, almost every known combustible.

— Joseph L. Proust, Recherches sur le bleu de Prusse, Journal de Physique...

At the end of the 18th century, when the concept of a chemical compound had not yet been fully developed, the law was novel. In fact, when first proposed, it was a controversial statement and was opposed by other chemists, most notably Proust's fellow Frenchman Claude Louis Berthollet, who argued that the elements could combine in any proportion. [3] The existence of this debate demonstrates that, at the time, the distinction between pure chemical compounds and mixtures had not yet been fully developed. [4]

The law of definite proportions contributed to the atomic theory that John Dalton promoted beginning in 1805, which explained matter as consisting of discrete atoms, 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. [5]

A related early idea was Prout's hypothesis, formulated by English chemist William Prout, who proposed that the hydrogen atom was the fundamental atomic unit. From this hypothesis was derived the whole number rule, 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 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, [6] with the mass defect caused by differing binding energies being significantly smaller.

Non-stoichiometric compounds and isotopes

Although very useful in the foundation of modern chemistry, the law of definite proportions is not universally true. There exist non-stoichiometric compounds whose elemental composition can vary from sample to sample. Such compounds follow the law of multiple proportion. An example is the iron oxide wüstite, 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 it is about Fe0.95O due to crystallographic vacancies. 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 since astronomical, atmospheric, oceanic, crustal and deep Earth processes may concentrate some environmental isotopes preferentially. With the exception of hydrogen and its isotopes, the effect is usually small, but is measurable with modern-day instrumentation.

Many natural polymers vary in composition (for instance DNA, proteins, carbohydrates) 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.

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<span class="mw-page-title-main">Atom</span> Smallest unit of a chemical element

Atoms are the basic particles of the chemical elements. An atom consists of a nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished from each other by the number of protons that are in their atoms. For example, any atom that contains 11 protons is sodium, and any atom that contains 29 protons is copper. Atoms with the same number of protons but a different number of neutrons are called isotopes of the same element.

<span class="mw-page-title-main">History of atomic theory</span>

Atomic theory is the scientific theory that matter is composed of particles called atoms. The definition of the word "atom" has changed over the years in response to scientific discoveries. Initially, it referred to a hypothetical concept of there being some fundamental particle of matter, too small to be seen by the naked eye, that could not be divided. Then the definition was refined to being the basic particles of the chemical elements, when chemists observed that elements seemed to combine with each other in ratios of small whole numbers. Then physicists discovered that these particles had an internal structure of their own and therefore perhaps did not deserve to be called "atoms", but renaming atoms would have been impractical by that point.

<span class="mw-page-title-main">Law of multiple proportions</span> 1804 observation in physical chemistry

In chemistry, the law of multiple proportions states that in compounds which contain two particular chemical elements, the amount of Element A per measure of Element B will differ across these compounds by ratios of small whole numbers. For instance, the ratio of the hydrogen content in methane (CH4) and ethane (C2H6) per measure of carbon is 4:3. This law is also known as Dalton's Law, named after John Dalton, the chemist who first expressed it. The discovery of this pattern led Dalton to develop the modern theory of atoms, as it suggested that the elements combine with each other in multiples of a basic quantity. Along with the law of definite proportions, the law of multiple proportions forms the basis of stoichiometry.

<span class="mw-page-title-main">Stoichiometry</span> Calculation of relative weights of reactants and products in chemical reactions

Stoichiometry is the relationships among the weights of reactants and products before, during, and following chemical reactions.

<span class="mw-page-title-main">Mole (unit)</span> SI unit of amount of substance

The mole (symbol mol) is a unit of measurement, the base unit in the International System of Units (SI) for amount of substance, a quantity proportional to the number of elementary entities of a substance. One mole contains exactly 6.02214076×1023 elementary entities (approximately 602 sextillion or 602 billion times a trillion), which can be atoms, molecules, ions, ion pairs, or other particles. The number of particles in a mole is the Avogadro number (symbol N0) and the numerical value of the Avogadro constant (symbol NA) expressed in mol-1. The value was chosen on the basis of the historical definition of the mole as the amount of substance that corresponds to the number of atoms in 12 grams of 12C, which made the mass of a mole of a compound expressed in grams, numerically equal to the average molecular mass or formula mass of the compound expressed in daltons. With the 2019 revision of the SI, the numerical equivalence is now only approximate but may be assumed for all practical purposes.

The dalton or unified atomic mass unit is a unit of mass defined as ⁠1/12⁠ of the mass of an unbound neutral atom of carbon-12 in its nuclear and electronic ground state and at rest. It is a non-SI unit accepted for use with SI. The atomic mass constant, denoted mu, is defined identically, giving mu = ⁠1/12⁠m(12C) = 1 Da.

<span class="mw-page-title-main">Molar mass</span> Mass per amount of substance

In chemistry, the molar mass of a chemical compound is defined as the ratio between the mass and the amount of substance of any sample of the compound. The molar mass is a bulk, not molecular, property of a substance. The molar mass is an average of many instances of the compound, which often vary in mass due to the presence of isotopes. Most commonly, the molar mass is computed from the standard atomic weights and is thus a terrestrial average and a function of the relative abundance of the isotopes of the constituent atoms on Earth. The molar mass is appropriate for converting between the mass of a substance and the amount of a substance for bulk quantities.

<span class="mw-page-title-main">Joseph Proust</span> French chemist

Joseph Louis Proust was a French chemist. He was best known for his discovery of the law of definite proportions in 1797, stating that chemical compounds always combine in constant proportions.

<span class="mw-page-title-main">Amount of substance</span> Ratio of the number of particles in a sample to Avogadros constant

In chemistry, the amount of substance (symbol n) in a given sample of matter is defined as a ratio (n = N/NA) between the number of elementary entities (N) and the Avogadro constant (NA). The entities are usually molecules, atoms, ions, or ion pairs of a specified kind. The particular substance sampled may be specified using a subscript, e.g., the amount of sodium chloride (NaCl) would be denoted as nNaCl. The unit of amount of substance in the International System of Units is the mole (symbol: mol), a base unit. Since 2019, the value of the Avogadro constant NA is defined to be exactly 6.02214076×1023 mol−1. Sometimes, the amount of substance is referred to as the chemical amount or, informally, as the "number of moles" in a given sample of matter.

<span class="mw-page-title-main">History of chemistry</span>

The history of chemistry represents a time span from ancient history to the present. By 1000 BC, civilizations used technologies that would eventually form the basis of the various branches of chemistry. Examples include the discovery of fire, extracting metals from ores, making pottery and glazes, fermenting beer and wine, extracting chemicals from plants for medicine and perfume, rendering fat into soap, making glass, and making alloys like bronze.

In chemistry, equivalent weight is the mass of one equivalent, that is the mass of a given substance which will combine with or displace a fixed quantity of another substance. The equivalent weight of an element is the mass which combines with or displaces 1.008 gram of hydrogen or 8.0 grams of oxygen or 35.5 grams of chlorine.

Chemical laws are those laws of nature relevant to chemistry. The most fundamental concept in chemistry is the law of conservation of mass, which states that there is no detectable change in the quantity of matter during an ordinary chemical reaction. Modern physics shows that it is actually energy that is conserved, and that energy and mass are related; a concept which becomes important in nuclear chemistry. Conservation of energy leads to the important concepts of equilibrium, thermodynamics, and kinetics.

<span class="mw-page-title-main">Non-stoichiometric compound</span> Chemical compounds that cannot be represented by an empirical formula

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 ; most often, in such materials, some small percentage of atoms are missing or too many atoms are packed into an otherwise perfect lattice work.

<span class="mw-page-title-main">Chemical substance</span> Form of matter

A chemical substance is a unique form of matter with constant chemical composition and characteristic properties. Chemical substances may take the form of a single element or chemical compounds. If two or more chemical substances can be combined without reacting, they may form a chemical mixture. If a mixture is separated to isolate one chemical substance to a desired degree, the resulting substance is said to be chemically pure.

<span class="mw-page-title-main">Mass (mass spectrometry)</span> Physical quantities being measured

The mass recorded by a mass spectrometer can refer to different physical quantities depending on the characteristics of the instrument and the manner in which the mass spectrum is displayed.

<span class="mw-page-title-main">Whole number rule</span> Rule of thumb in chemistry

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 multiples of the weight of the hydrogen atom. It is also known as the Aston whole number rule after Francis W. Aston who was awarded the Nobel Prize in Chemistry in 1922 "for his discovery, by means of his mass spectrograph, of isotopes, in a large number of non-radioactive elements, and for his enunciation of the whole-number rule."

<span class="mw-page-title-main">Atomic mass</span> Rest mass of an atom in its ground state

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<span class="mw-page-title-main">Chemical compound</span> Substance composed of multiple chemically bonded elements

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<span class="mw-page-title-main">Jöns Jacob Berzelius</span> Swedish chemist (1779–1848)

Baron Jöns Jacob Berzelius (Swedish:[jœnsˈjɑ̌ːkɔbbæˈʂěːlɪɵs] was a Swedish chemist. In general, he is considered the last person to know the whole field of chemistry. Berzelius is considered, along with Robert Boyle, John Dalton, and Antoine Lavoisier, to be one of the founders of modern chemistry. Berzelius became a member of the Royal Swedish Academy of Sciences in 1808 and served from 1818 as its principal functionary. He is known in Sweden as the "Father of Swedish Chemistry". During his lifetime he did not customarily use his first given name, and was universally known simply as Jacob Berzelius.

The law of reciprocal proportions, also called law of equivalent proportions or law of permanent ratios, is one of the basic laws of stoichiometry.

References

  1. ↑ Zumdahl, S. S. “Chemistry” Heath, 1986: Lexington, MA. ISBN   0-669-04529-2.
  2. ↑ Proust, J. L. (1794 [i.e., 1797]). "Extrait d'un mémoire intitulé : Recherches sur le bleu de Prusse". Journal de Physique, de Chimie, d'Histoire Naturelle et des Arts.45: 334-341 (specifically, p. 341). Although Proust's article appeared in a volume dated 1794, the volume was actually printed in 1797, as can be seen from the article published in the same issue on p. 314.
  3. ↑ Dalton, J. (1808). op. cit., ch. II, that Berthollet held the opinion that in all chemical unions, there exist insensible gradations in the proportions of the constituent principles.
  4. ↑ Proust argued that compound applies only to materials with fixed proportions: Proust, J.-L. (1806). Sur les mines de cobalt, nickel et autres, Journal de Physique, 63:566-8. Excerpt Archived 2022-01-21 at the Wayback Machine , from Maurice Crosland, ed., The Science of Matter: a Historical Survey, Harmondsworth, UK: Penguin, 1971. Accessed 2008-05-08.
  5. ↑ Dalton, J. (1808). A New System of Chemical Philosophy, volume 1, Manchester. Excerpt Archived 2021-10-06 at the Wayback Machine . Accessed 2008-05-08.
  6. ↑ Gamow, George (1987). One Two Three... Infinity: Facts and Speculations of Science (Bantam Science and Mathematics ed.). Bantam. pp. 151–154. ISBN   978-0486256641.
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