Hydrogen iodide

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Hydrogen iodide

Names

IUPAC name

Iodane

Other names

Hydroiodic acid (aqueous solution)

Iodine hydride

Identifiers

CAS Number  10034-85-2 

3D model (JSmol)  Interactive image

ChemSpider  23224 
ECHA InfoCard 100.030.087 

PubChem CID  24841

RTECS number  MW3760000

UNII  694C0EFT9Q 

CompTox  DTXSID2044349 
Dashboard (EPA)

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InChI

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SMILES

Properties

Chemical formula HI

Molar mass 127.904 g/mol

Appearance Colorless gas

Density 2.85 g/mL (-47 °C)

Melting point −50.80 °C (−59.44 °F; 222.35 K)

Boiling point −35.36 °C (−31.65 °F; 237.79 K)

Solubility in water approximately 245 g/100 ml

Acidity (pKa) -10 (in water, estimate);[1] -9.5 (±1.0) [2]

2.8 (in acetonitrile)[3]

Conjugate acid Iodonium

Conjugate base Iodide

Structure

Molecular shape Terminus

Dipole moment 0.38 D

Hazards

Main hazards Toxic, corrosive, Harmful and Irritant

Safety data sheet See: data page

 hydrogen iodide

hydroiodic acid

R-phrases (outdated) R20, R21, R22, R35

S-phrases (outdated) S7, S9, S26, S45

NFPA 704 (fire diamond)

3
0
1
COR

Flash point Non-flammable

Related compounds

Other anions Hydrogen fluoride

Hydrogen chloride

Hydrogen bromide

Hydrogen astatide

Supplementary data page

Structure and Refractive index (n),

properties
Dielectric constant (εr), etc.

Thermodynamic Phase behaviour

data
solid–liquid–gas

Spectral data UV, IR, NMR, MS

Except where otherwise noted, data are given for materials in

their standard state (at 25 °C [77 °F], 100 kPa).

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Infobox references

Hydrogen iodide (HI) is a diatomic molecule and hydrogen halide. Aqueous

solutions of HI are known as hydroiodic acid or hydriodic acid, a strong acid.
Hydrogen iodide and hydroiodic acid are, however, different in that the former is a gas
under standard conditions, whereas the other is an aqueous solution of the gas. They
are interconvertible. HI is used in organic and inorganic synthesis as one of the primary
sources of iodine and as a reducing agent.
 Contents

 1Properties of hydrogen iodide

o 1.1Hydroiodic acid
 2Synthesis
 3Key reactions and applications
 4References
 5External links

Properties of hydrogen iodide[edit]

HI is a colorless gas that reacts with oxygen to give water and iodine. With moist air, HI
gives a mist (or fumes) of hydroiodic acid. It is exceptionally soluble in water, giving
hydroiodic acid. One liter of water will dissolve 425 liters of HI gas, the most
concentrated solution having only four water molecules per molecule of HI. [4]
Hydroiodic acid[edit]
Hydroiodic acid is not pure hydrogen iodide, but a mixture containing it. Commercial
"concentrated" hydroiodic acid usually contains 48–57% HI by mass. The solution forms
an azeotrope boiling at 127 °C with 57% HI, 43% water. The high acidity is caused by
the dispersal of the ionic charge over the anion. The iodide ion radius is much larger
than the other common halides, which results in the negative charge being dispersed
over a large space. By contrast, a chloride ion is much smaller, meaning its negative
charge is more concentrated, leading to a stronger interaction between the proton and
the chloride ion. This weaker H+···I− interaction in HI facilitates dissociation of the proton
from the anion and is the reason HI is the strongest acid of the hydrohalides.
HI(g) + H
2O(l) → H

3O
+

(aq) + I−(aq) Ka ≈ 1010

HBr(g) + H
2O(l) → H

3O
+

(aq) + Br−(aq) Ka ≈ 109

HCl(g) + H
2O(l) → H

3O
+

(aq) + Cl−(aq) Ka ≈ 106

Synthesis[edit]
The industrial preparation of HI involves the reaction of I 2 with hydrazine,
which also yields nitrogen gas:[5]
2 I2 + N
2H

4 → 4 HI + N

When performed in water, the HI must be distilled.

HI can also be distilled from a solution of NaI or other alkali iodide in
concentrated phosphoric acid (note that concentrated sulfuric acid will not
work for acidifying iodides, as it will oxidize the iodide to elemental
iodine).
Another way HI may be prepared is by bubbling hydrogen sulfide steam
through an aqueous solution of iodine, forming hydroiodic acid (which is
distilled) and elemental sulfur (this is filtered): [6]
H2S + I2 → 2 HI + S
Additionally, HI can be prepared by simply combining H 2 and I2:
H2 + I2 → 2 HI
This method is usually employed to generate high-purity samples.
For many years, this reaction was considered to involve a simple
bimolecular reaction between molecules of H 2 and I2. However,
when a mixture of the gases is irradiated with the wavelength of
light equal to the dissociation energy of I2, about 578 nm, the rate
increases significantly. This supports a mechanism whereby I 2 first
dissociates into 2 iodine atoms, which each attach themselves to
a side of an H2 molecule and break the H−H bond:[7]
In the laboratory, another method involves hydrolysis of PI3, the
iodine equivalent of PBr3. In this method, I2 reacts
with phosphorus to create phosphorus triiodide, which then
reacts with water to form HI and phosphorous acid:
3 I2 + 2 P + 6 H
2O → 2 PI3 + 6 H

2O → 6 HI + 2 H3PO3

Key reactions and applications[edit]

Solutions of hydrogen iodide are easily oxidized by air:
4 HI + O2 → 2 H
2O + 2 I2

HI + I2 → HI3
HI
3 is dark brown in color, which makes aged

solutions of HI often appear dark brown.

Like HBr and HCl, HI adds to alkenes:[8]
HI + H2C=CH2 → H
3CCH

2I

HI is also used in organic chemistry to

convert primary alcohols into alkyl halides.[9] This
reaction is an SN2 substitution, in which the
iodide ion replaces the "activated" hydroxyl
group (water):

HI is preferred over other hydrogen halides

because the iodide ion is a much better
nucleophile than bromide or chloride, so the
reaction can take place at a reasonable rate
without much heating. This reaction also
occurs for secondary and tertiary alcohols,
but substitution occurs via the SN1 pathway.
HI (or HBr) can also be used to
cleave ethers into alkyl iodides and alcohols,
in a reaction similar to the substitution of
alcohols. This type of cleavage is significant
because it can be used to convert a
chemically stable[9] and inert ether into more
reactive species. In this example diethyl
ether is split into ethanol and iodoethane:

The reaction is regioselective, as iodide

tends to attack the less sterically
hindered ether carbon.
HI is subject to the
same Markovnikov and anti-Markovnikov
guidelines as HCl and HBr.
Although harsh by modern standards, HI
was commonly employed as a reducing
agent early on in the history of organic
chemistry. Chemists in the 19th century
attempted to prepare cyclohexane by HI
reduction of benzene at high
temperatures, but instead isolated the
rearranged product, methylcyclopentane
(see the article on cyclohexane). As first
reported by Kiliani,[10] hydroiodic acid
reduction of sugars and other polyols
results in the reductive cleavage of
several or even all hydroxy groups,
although often with poor yield and/or
reproducibility.[11] In the case of benzyl
alcohols and alcohols with α-carbonyl
groups, reduction by HI can provide
synthetically useful yields of the
corresponding hydrocarbon product
(ROH + 2HI → RH + H
2O + I2).  This process can be made
[8]

catalytic in HI using red phosphorus to

reduce the formed I2.[12]