402 IODINE HEPTAFLUORIDE
Iodide ion may be measured by amperometric titration and, more accurately, by ion chromatography.
Toxicity
Iodine vapors are an irritant to eyes, nose and mucous membranes. Inhalation can cause headache, irritation, and congestion of lungs. Oral intake can produce burning of the mouth, vomiting, diarrhea, and abdominal cramps. Skin contact can cause rashes.
IODINE HEPTAFLUORIDE
[16921-96-3]
Formula: IF7; MW 221.90; pentagonal bipyramidal structure. Synonym: heptafluoroiodine
Uses
Iodine heptafluoride is used as a fluorinating agent.
Physical Properties
Colorless gas; mold-like pungent odor; melting point 6.45°C; sublimes at 4.77°C; supercools to a colorless liquid that boils at 4.5°C; liquid density 2.8g/mL at 6°C; soluble in water.
Preparation
Iodine heptafluoride may be prepared by the reaction of fluorine with potassium iodide:
KI + 4F2 → IF7 + KF
Dried KI should be used to minimize the formation of IOF5.
Also, IF7 can be prepared by passing fluorine gas through liquid iodine pentafluoride at high temperature (90°C) and then heating the vapors to 270°C to complete the reaction:
IF5 + F2 → IF7
Reactions
Most reactions of iodine heptafluoride are similar to those of iodine pentafluoride, except that it does not undergo any further fluorine addition reactions (See Iodine Pentafluoride). The compound reacts with a number of inorganic substances, forming their fluorides, and forms fluoro-derivatives with organics when in diluted form.
Toxicity
The compound is corrosive. Vapors are highly irritating to eyes and mucous
IODINE MONOCHLORIDE 403
membranes.
IODINE MONOCHLORIDE
[7790-99-0]
Formula: ICl; MW 162.357
Synonyms: Wijs’ chloride; iodine chloride
Uses
Iodine monochloride is used as an analytical reagent to determine iodine values of oils and fats. It is dissolved in glacial acetic acid (Wijs’ solution) for the analysis. ICl is used in organic synthesis. It also is used as a topical antiseptic.
Physical Properties
Black crystalline solid; exists in two modifications: stable black needles known as alpha form that produces ruby-red color in transmitted light, and a labile, metastable beta modification consisting of black platelets which appear brownish-red in transmitted light; density of alpha form 3.86 g/cm3 at 0°C; density of beta form 3.66 g/cm3 at 0°C; alpha form melts at 27.3°C, vapor pressure being 28 torr at 25°C; beta form melts at 13.9°C; liquid iodine monochloride has bromine-like reddish-brown color; liquid density 3.10 g/mL at 29°C; viscosity 1.21 centipoise at 35°C; decomposes around 100°C; supercools below its melting point; polar solvent; as a liquid it dissolves iodine, ammonium chloride and alkali metal chlorides; liquid ICl also miscible with carbon tetrachloride, acetic acid and bromine; the solid crystals dissolve in ethanol, ether, acetic acid and carbon disulfide; solid ICl also dissolves in conc. HCl but decomposes in water or dilute HCl.
Thermochemical Properties |
|
|
|
∆Ηƒ° (liq) |
–5.712 kcal/mol |
||
∆Ηƒ° (gas) |
4.254 kcal/mol |
||
∆Gƒ°(liq) |
–3.250 kcal/mol |
||
∆Gƒ° (gas) |
–1.315 kcal/mol |
||
S° |
(liq) |
32.29 cal/degree mol |
|
S° |
(gas) |
59.18 cal/degree mol |
|
Cρ (liq) |
0.0257 cal/degree mol |
||
Cρ (gas) |
8.51 cal/degree mol |
||
∆Hfus |
2.77 |
kcal/mol |
|
∆Hvap |
9.95 |
kcal/mol |
|
Preparation
Iodine monochloride is prepared by the action of liquid or dry chlorine on a stoichiometric quantity of solid iodine. Aqueous solutions of ICl are prepared by passing chlorine gas into a suspension of iodine in moderately strong hydrochloric acid:
404 IODINE MONOCHLORIDE
5I2 + 4HCl + 3Cl2 → 10ICl + 2H2
Alternatively, iodine monochloride may be made by oxidation of iodine with iodic acid in strong hydrochloric acid solution:
2I2 + HIO3 + 2HCl → 2ICl + 3HIO
Reactions
When vaporized at 100°C iodine monochloride decomposes to chlorine and iodine:
2ICl → I2 + Cl2
Heating with hydrogen at elevated temperatures yields hydrogen chloride and hydrogen iodide:
ICl + H2 → HCl + HI
Reactions with metals in a finely-divided state or at elevated temperatures, produce metal chlorides and metal iodides:
3Al + 3ICl → AlCl3 + AlI3
It hydrolizes in water, decomposing to iodine, hydrochloric acid and iodic acid:
5ICl + 3H2O → 2I2 + 5HCl + HIO3
Under milder conditions and in equimolar ratio, hypoiodous acid forms:
ICl + H2O → HIO + HCl
Similar hydrolysis occurs in dilute HCl.
Reactions with alkanes produce iodo derivatives and hydrogen chloride:
C4H10 + ICl → C4H9I + HCl
Iodine monochloride adds to unsaturated compounds. Some examples are:
CH2=CH2 + ICl → ICH2CH2Cl
CH3CH=CH2 + ICl → CH3CHClCH2I
CH≡CH + ICl → ClCH=CHI
Analysis
Elemental composition: Cl 21.84%, I 78.16%. The compound is hydrolyzed in water and the product chloride and iodate ions are analyzed by ion chro-
IODINE PENTAFLUORIDE 405
matography. Iodine is separated by filtration and measured by gravimetry or by the Leuco Crystal violet colorimetric method (See Iodine). Alternatively, the liquid or solid compound is dissolved in organic solvent, diluted appropriately, and analyzed by GC/MS.
IODINE PENTAFLUORIDE
[7783-66-6]
Formula: IF5; MW 221.90; square pyramidal structure.
Uses
Iodine pentafluoride is a fluorinating agent. It also is used in incendiaries.
Physical Properties
Colorless to yellowish liquid; fumes in air; density 3.19 g/mL; freezes at 9.43°C; boils at 100.5°C; reacts with water.
Thermochemical Properties |
|
∆Hf° (l) |
–206.7 kcal/mol |
∆Hf° (g) |
–196.6 kcal/mol |
∆Gf° (g) |
–179.7 kcal/mol |
S° (g) |
78.3 cal/degree mol |
Cρ |
23.7 cal/degree mol |
∆Hvap |
9.87 kcal/mol |
Preparation
Iodine pentafluoride is best obtained by passing fluorine gas over iodine under cooling conditions:
I2 + 5F2 → 2IF5
Also, it may be prepared by the reaction of fluorine with iodine trifluoride; or heating potassium iodide with a stoichiometric amount of fluorine:
IF3 + F2 → IF5
KI + 3F2 → KF + IF5
Reactions
Thermal dissociation of iodine pentafluoride yields iodine trifluoride and fluorine:
IF5 → IF3 + F2
It combines with fluorine, forming iodine heptafluoride: IF5 + F2 → IF7
406 IODINE PENTAFLUORIDE
Iodine pentafluoride similar to other halogen fluorides exhibits amphoteric behavior; i.e., with strong Lewis acids, such as SbF5, it can form cation, IF4+:
IF5 + SbF5 → IF4+SbF6¯
Similarly, with strong bases like potassium fluoride, it forms the anion IF6¯:
IF5 + KF → K+IF6¯
Iodine pentafluoride reacts with many inorganic substances, forming their fluorides. Such inorganic substances include metals, metal oxides and several nonmetals. Some examples are:
Zn + IF5 → ZnF2 + IF3
2Al2O3 + 3IF5 → 4AlF3 + 3IF + 3O2
2P4 + 2IF5 → 8PF5 + I2
It reacts violently with water, forming hydrogen fluoride and iodic acid:
IF5 + 3H2O → 5HF + HIO3
Iodine pentafluoride reacts with organic substances, forming their fluoroderivatives only when it is diluted with nitrogen. The pure compound may otherwise carbonize organics on contact, sometimes violently.
Analysis
Elemental composition: I 57.19%, F 42.81%. The compound may be hydrolyzed with water slowly and cautiously (a violent reaction occurs). Iodate anion may be measured by redox titration and the fluoride ion by using a fluoride ion-selective electrode. Alternatively, these anions in their aqueous solution may be determined by ion chromatography after appropriate dilution.
Hazard
Most reactions are violent. Accidental contact with a number of organics and inorganic substances may present a fire or explosion hazard. Rapid mixing with water can be explosive. The compound is highly corrosive. Skin contact can cause a severe burn. Vapors are highly irritating to eyes, nose and mucous membranes. (Patnaik, P. 1999. A Comprehensive Guide to the Hazardous Properties of Chemical Substances, 2nd. Ed. New York: John Wiley & Sons.)