Ammonium Bifluoride
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Ammonium bifluoride is an
inorganic compound An inorganic compound is typically a chemical compound that lacks carbon–hydrogen bonds⁠that is, a compound that is not an organic compound. The study of inorganic compounds is a subfield of chemistry known as ''inorganic chemistry''. Inorgan ...
with the formula or . It is produced from
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
and
hydrogen fluoride Hydrogen fluoride (fluorane) is an Inorganic chemistry, inorganic compound with chemical formula . It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluori ...
. This colourless salt is a glass- etchant and an intermediate in a once-contemplated route to
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
.


Structure

Ammonium bifluoride, as its name indicates, contains an
ammonium Ammonium is a modified form of ammonia that has an extra hydrogen atom. It is a positively charged (cationic) polyatomic ion, molecular ion with the chemical formula or . It is formed by the protonation, addition of a proton (a hydrogen nucleu ...
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 ...
(), and a
bifluoride The bifluoride ion is an inorganic anion with the chemical formula . The anion is colorless. Salts of bifluoride are commonly encountered in the reactions of fluoride salts with hydrofluoric acid. The commercial production of fluorine involves ...
(or hydrogen difluoride)
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 conven ...
(). The triatomic bifluoride anion features a strong
three-center four-electron bond The 3-center 4-electron (3c–4e) bond is a model used to explain bonding in certain hypervalent molecules such as tetratomic and hexatomic interhalogen compounds, sulfur tetrafluoride, the xenon fluorides, and the bifluoride ion. It is also k ...
(specifically, a
symmetrical hydrogen bond A symmetric hydrogen bond is a special type of hydrogen bond in which the proton is spaced exactly halfway between two identical atoms. The strength of the bond to each of those atoms is equal. It is an example of a 3-center 4-electron bond. This ...
) with a bond energy greater than 155 kJ/mol, and an H-F length of 114 pm. In solid form (), ammonium biflouride is similar to other
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
salts. Its
crystal system In crystallography, a crystal system is a set of point groups (a group of geometric symmetries with at least one fixed point). A lattice system is a set of Bravais lattices (an infinite array of discrete points). Space groups (symmetry groups ...
is considered
orthorhombic In crystallography, the orthorhombic crystal system is one of the 7 crystal systems. Orthorhombic Lattice (group), lattices result from stretching a cubic crystal system, cubic lattice along two of its orthogonal pairs by two different factors, res ...
, with each cation coordinated with four anions in a tetrahedron (and vice versa). Hydrogen atoms in the ammonium ion form
hydrogen bonds In chemistry, a hydrogen bond (H-bond) is a specific type of molecular interaction that exhibits partial covalent character and cannot be described as a purely electrostatic force. It occurs when a hydrogen (H) atom, covalently bonded to a mo ...
with the fluorine atoms, and in the resulting structure, N-H-F are roughly colinear. As a result of these hydrogen bonds, this crystal structure varies from those of other bifluoride salts, such as
potassium bifluoride Potassium bifluoride is the inorganic compound with the formula . This colourless salt consists of the potassium cation () and the bifluoride anion (). The salt is used as an etchant for glass. Sodium bifluoride is related and is also of commerci ...
and rubidium bifluoride. Its crystals are unstable, and decompose rapidly when exposed to air.


Production and applications

Ammonium bifluoride is a component of some etchants. It attacks
silica Silicon dioxide, also known as silica, is an oxide of silicon with the chemical formula , commonly found in nature as quartz. In many parts of the world, silica is the major constituent of sand. Silica is one of the most complex and abundant f ...
component of glass: :
Potassium bifluoride Potassium bifluoride is the inorganic compound with the formula . This colourless salt consists of the potassium cation () and the bifluoride anion (). The salt is used as an etchant for glass. Sodium bifluoride is related and is also of commerci ...
is a related more commonly used etchant. Ammonium bifluoride has been considered as an intermediate in the production of
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
from
hexafluorosilicic acid Hexafluorosilicic acid is an inorganic compound with the chemical formula . Aqueous solutions of hexafluorosilicic acid consist of salts of the cation and hexafluorosilicate anion. These salts and their aqueous solutions are colorless. Hexafluo ...
. Thus, hexafluorosilicic acid is hydrolyzed to give
ammonium fluoride Ammonium fluoride is the inorganic compound with the formula NH4F. It crystallizes as small colourless prisms, having a sharp saline taste, and is highly soluble in water. Like all fluoride salts, it is moderately toxic in both acute and chronic o ...
, which thermally decomposes to give the bifluoride: : : The resulting ammonium bifluoride is converted to sodium bifluoride, which thermally decomposes to release HF. Ammonium bifluoride is also used as an additive in tin-nickel plating processes as the fluoride ion acts as a complexing agent with the tin, allowing for greater control over the resulting composition and finish.


Toxicity

Ammonium bifluoride is toxic to consume and a skin corrosion agent. Upon exposure to skin, rinsing with water followed by a treatment of
calcium gluconate Calcium gluconate is the calcium salt of gluconic acid and is used as a mineral supplement and medication. As a medication it is used by injection into a vein to treat low blood calcium, high blood potassium, and magnesium toxicity. Supplem ...
is required. In water, ammonium bifluoride exists in
chemical equilibrium In a chemical reaction, chemical equilibrium is the state in which both the Reagent, reactants and Product (chemistry), products are present in concentrations which have no further tendency to change with time, so that there is no observable chan ...
with
hydrofluoric acid Hydrofluoric acid is a solution of hydrogen fluoride (HF) in water. Solutions of HF are colorless, acidic and highly corrosive. A common concentration is 49% (48–52%) but there are also stronger solutions (e.g. 70%) and pure HF has a boiling p ...
and heating releases
hydrogen fluoride Hydrogen fluoride (fluorane) is an Inorganic chemistry, inorganic compound with chemical formula . It is a very poisonous, colorless gas or liquid that dissolves in water to yield hydrofluoric acid. It is the principal industrial source of fluori ...
gas. Consequently, there is an equivalent toxicological risk as is present with hydrofluoric acid, and the same safety precautions apply. Ammonium bifluoride is used in some automotive wheel cleaning products. Many injuries have resulted in users not being aware of the risks posed by the products. Ammonium bifluoride based products are often considered a safer alternative to hydrofluoric acid, yet still pose clear risks to the handler. Ammonium bifluoride, ammonium fluoride, and hydrofluoric acid have been described as "too dangerous for any use in a car wash environment" by '' Professional Car Washing and Detailing'' magazine, advice that accords with a 2015 report from the U.S.
Centers for Disease Control and Prevention The Centers for Disease Control and Prevention (CDC) is the National public health institutes, national public health agency of the United States. It is a Federal agencies of the United States, United States federal agency under the United S ...
.


References

{{Ammonium salts Nonmetal halides Ammonium compounds Deliquescent materials Bifluorides