Chromium(I) hydride, systematically named chromium hydride, is an
inorganic compound with the
chemical formula
In chemistry, a chemical formula is a way of presenting information about the chemical proportions of atoms that constitute a particular chemical compound or molecule, using chemical element symbols, numbers, and sometimes also other symbol ...
(also written as or CrH). It occurs naturally in some kinds of stars where it has been detected by its spectrum. However, molecular chromium(I) hydride with the formula CrH has been isolated in solid gas matrices. The molecular hydride is very reactive. As such the compound is not well characterised, although many of its properties have been calculated via
computational chemistry.
Molecular forms
A. G. Gaydon first created CrH gas with an
electric arc
An electric arc, or arc discharge, is an electrical breakdown of a gas that produces a prolonged electrical discharge. The current through a normally nonconductive medium such as air produces a plasma; the plasma may produce visible light. An ...
between chromium electrodes in a hydrogen air flame.
CrH can be formed by the reaction of chromium metal vapour, created by an electrical discharge in the presence of hydrogen. The electric discharge breaks up the H
2 molecules into reactive H atoms. So the reaction then proceeds as Cr(g) + H
→ CrH.
Another method to make CrH is to react
chromium carbonyl (Cr(CO)
6) vapour with atomic hydrogen generated by an electric discharge.
Chromium hydride can also be formed by reacting chromium with methane in an electric arc. This also produces a variety of carbon and hydrogen containing chromium molecules such as CrCH
3 and CrCCH.
Also it is possible to trap CrH into a solid argon
noble gas matrix. The solid argon does not react with CrH and allows studying reactive molecules that need to be kept apart from other molecules. The researchers that produced the trapped CrH molecules also believe that they made and trapped CrH
2 molecules, based on its spectrum.
Properties
When produced in the reaction with chromium vapour in an electric discharge, the chromium hydride gas glows with a bright bluish-green colour.
The ground electronic state of CrH is
6Σ
+.
The outer
electronic configuration
In atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule (or other physical structure) in atomic or molecular orbitals. For example, the electron configuration of the neon atom ...
is σ
2σ
1δ
2π
2.
The σ
2 electron is the bonding electron with hydrogen, and the other electrons are
unpaired. The only part of the molecule with
nuclear spin, is the proton in the hydrogen.
Hyperfine structure of the spectral lines is extremely fine.
The
Fermi contact term which measures the hyperfine splitting is only -34.43 MHz, whereas for the hydrogen atom it is
1420.40575177 MHz.
The
dipole moment of the molecule is 3.864
Debye
The debye (symbol: D) (; ) is a CGS unit (a non- SI metric unit) of electric dipole momentTwo equal and opposite charges separated by some distance constitute an electric dipole. This dipole possesses an electric dipole moment whose value is g ...
.
The disassociation energy required to break the molecule into two atoms is 2.118 eV
or 1.93 eV.
The CrH molecule is strongly paramagnetic. It can have a lifetime of over 0.1 seconds when it is trapped in
3He cooled to 0.650 K.
Spectrum
Like other molecules, the CrH molecule can store energy in several ways. Firstly, the molecule can spin with the hydrogen atom seeming to orbit the chromium atom. Secondly, it can vibrate with the two atoms bouncing towards and away from each other. Thirdly, electrons can change from one
atomic orbital
In atomic theory and quantum mechanics, an atomic orbital is a function describing the location and wave-like behavior of an electron in an atom. This function can be used to calculate the probability of finding any electron of an atom in an ...
to another in the chromium atom. All of these can happen at the same time. All the numerous combinations of changes result in many different possible energy changes. Each of these changes will match a frequency in the electromagnetic spectrum which is absorbed. When many of these frequencies cluster together in a group, an absorption band results.
An ultraviolet spectral band between 360 and 370 nm was discovered in 1937.
A
6Σ
+–X
6Σ
+ transition is observed in S type stars and sunspots and also L type brown dwarfs.
Submillimeter
Changes in the rotational rate of the molecule lead to a far-infrared spectrum. N=1
→0 transition has line frequencies at 5/2 → 3/2 337.259145 GHz, 5/2 → 7/2 362.617943 GHz and 362.627794 GHz, and 5/2 → 5/2 396.541818 GHz and 396.590874 GHz. N=2
→1 735 GHz; N=3
→2 at 1.11 THz N=4
→3 at 1.47 THz
Kleman & Uhler observed the infrared spectrum and were the first to note absorption bands.
Occurrence in stars
The existence of CrH in stars was only established in 1980 when spectral lines were identified in
S-type star
An S-type star (or just S star) is a cool giant with approximately equal quantities of carbon and oxygen in its atmosphere. The class was originally defined in 1922 by Paul Merrill for stars with unusual absorption lines and molecular bands no ...
s and sunspots.
CrH was discovered in brown dwarfs in 1999. Along with
FeH, CrH became useful in classifying
L dwarfs.
The CrH spectrum was identified in a large sunspot in 1976, but the lines are much less prominent than FeH.
Concentration of CrH in the L5 type of brown dwarf is 3 parts per billion compared to H, whereas the normal abundance of chromium is 0.5 parts per million compared to Hydrogen.
In
S-type star
An S-type star (or just S star) is a cool giant with approximately equal quantities of carbon and oxygen in its atmosphere. The class was originally defined in 1922 by Paul Merrill for stars with unusual absorption lines and molecular bands no ...
s a series of unknown lines appeared in the near infrared spectrum. They were termed the Keenan bands based on a spectrum of
R Cyg. One of the bands with a band head at 861.11 nm was identified as due to CrH.
[ full text available]
CrH is used to classify the L-type brown dwarfs into subtypes L0 to L8. The CrH absorption band is a diagnostic feature of L-type stars. For subtypes of the L-type brown dwarfs, L5 to L8 the CrH band at 861.1 nm is more prominent than the FeH band at 869.2 nm and for L4 these two bands are equally strong. For L0 type stars,
TiO lines are similar in strength to CrH lines, and in L1 Ti0 lines are slightly weaker than CrH. L1 to L3 have FeH band stronger than the CrH.
Chromium(II) hydride
A related chemical compound, is the more stable
chromium(II) hydride, identified by Weltner ''et al.'' in 1979 using a solid argon matrix.
This compound is susceptible to dimerisation in the gas phase. The dimer is more stable than the monomer by 121 kJ mol
−1.
Chromium(II) hydride is the most hydrogenated, groundstate classical hydride of chromium.
[ CrH2 is predicted to be bent, rather than linear in shape.]
Non-classical hydrides
Other nonclassical hydrides also exist. They include dihydrogen molecules as a ligand, such as CrH(H2), CrH2(H2), CrH2(H2)2.
References
{{Hydrides by group
Chromium compounds
Metal hydrides