The nitrogen rule states that

organic compound In chemistry, organic compounds are generally any chemical compounds that contain carbon- hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. Th ...

s containing exclusively

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 ...

carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon makes ...

nitrogen Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seve ...

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 we ...

silicon Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic ...

phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ea ...

sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...

, and the halogens either have (1) an ''odd nominal mass'' that indicates an ''

odd number In mathematics, parity is the property of an integer of whether it is even or odd. An integer is even if it is a multiple of two, and odd if it is not.. For example, −4, 0, 82 are even because \begin -2 \cdot 2 &= -4 \\ 0 \cdot 2 &= 0 \\ 41 ...

'' of nitrogen atoms are present or (2) an ''even nominal mass'' that indicates an ''

even number In mathematics, parity is the property of an integer of whether it is even or odd. An integer is even if it is a multiple of two, and odd if it is not.. For example, −4, 0, 82 are even because \begin -2 \cdot 2 &= -4 \\ 0 \cdot 2 &= 0 \\ 4 ...

'' of nitrogen atoms in the molecular formula of the neutral compound. The nitrogen rule is not a rule as much as a general principle which may prove useful when attempting to solve organic

mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a '' mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is u ...

structures.

Formulation of the rule

This rule is derived from the fact that, perhaps coincidentally, for the most common

chemical elements A chemical element is a species of atoms that have a given number of protons in their nuclei, including the pure substance consisting only of that species. Unlike chemical compounds, chemical elements cannot be broken down into simpler sub ...

in neutral

s (hydrogen, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens), elements with even numbered nominal masses form even numbers of covalent bonds, while elements with

ed nominal masses form odd numbers of covalent bonds, with the exception of nitrogen, which has a nominal (or

integer An integer is the number zero (), a positive natural number (, , , etc.) or a negative integer with a minus sign ( −1, −2, −3, etc.). The negative numbers are the additive inverses of the corresponding positive numbers. In the language ...

)

mass Mass is an intrinsic property of a body. It was traditionally believed to be related to the quantity of matter in a physical body, until the discovery of the atom and particle physics. It was found that different atoms and different element ...

of 14, but has a

valency Valence or valency may refer to: Science * Valence (chemistry), a measure of an element's combining power with other atoms * Degree (graph theory), also called the valency of a vertex in graph theory * Valency (linguistics), aspect of verbs re ...

of 3. The nitrogen rule is only true for neutral structures in which all of the

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 in the molecule have a number of covalent bonds equal to their standard valency (counting each

sigma bond In chemistry, sigma bonds (σ bonds) are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools o ...

and

pi bond In chemistry, pi bonds (π bonds) are covalent chemical bonds, in each of which two lobes of an orbital on one atom overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbita ...

as a separate covalent bond for the purposes of the calculation). Therefore, the rule is typically only applied to the molecular ion signal in the

mass spectrum A mass spectrum is a histogram plot of intensity vs. '' mass-to-charge ratio'' (''m/z'') in a chemical sample, usually acquired using an instrument called a ''mass spectrometer''. Not all mass spectra of a given substance are the same; for examp ...

. Mass spectrometry generally operates by measuring the mass of

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 ...

s. If the measured ion is generated by creating or breaking a single covalent bond (such as protonating an

amine In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituent su ...

to form an

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 quaternar ...

center or removing a

hydride In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of ...

from a

molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bio ...

to leave a positively charged ion) then the nitrogen rule becomes reversed (odd numbered masses indicate even numbers of nitrogens and vice versa). However, for each consecutive covalent bond that is broken or formed, the nitrogen rule again reverses. Therefore, a more rigorous definition of the nitrogen rule for

s containing exclusively hydrogen, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens would be as follows: An even nominal mass indicates that a net even number of covalent bonds have been broken or formed and an even number of nitrogen atoms are present, or that a net odd number of covalent bonds have been broken or formed and an odd number of nitrogen atoms are present. An odd nominal mass indicates that a net even number of covalent bonds have been broken or formed and an odd number of nitrogen atoms are present, or that a net odd number of covalent bonds have been broken or formed and an even number of nitrogen atoms are present. Inorganic molecules do not necessarily follow the rule. For example, the nitrogen oxides NO and NO₂ have an odd number of nitrogens but even masses of 30 and 46, respectively.

References

{{Reflist Mass spectrometry Parity (mathematics)

Rule Rule or ruling may refer to: Education * Royal University of Law and Economics (RULE), a university in Cambodia Human activity * The exercise of political or personal control by someone with authority or power * Business rule, a rule pert ...

Nuclear chemistry

Formulation of the rule

See also

References