Potassium dichromate

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Potassium dichromate
IUPAC name	Potassium dichromate(VI)
Other names	Potassium bichromate
Identifiers
CAS number	[7778-50-9]
EINECS number	231-906-6
RTECS number	HX7680000
Properties
Molecular formula	K2Cr2O7
Molar mass	294.19 g/mol
Appearance	Red-orange crystalline solid
Density	2.676 g/cm3, solid
Melting point	398°C
Boiling point	500°C decomp.
Solubility in water	4.9 g/100 ml (0°C)
Structure
Crystal structure	Triclinic (α-form,<241.6 °C
Coordination geometry	Tetrahedral (for Cr)
Thermochemistry
Std enthalpy of formation ΔfHo298	-2033 kJ/mol
Standard molar entropy So298	291,2 J.K−1.mol−1
Hazards
Main hazards	Highly toxic Carc. Cat. 1 Muta. Cat. 2 Repr. Cat. 2 Oxidant Dangerous for the environment
R-phrases	R45, R46, R60, R61, R8, R21, R25, R26, R34, R42/43, R48/23, R50/53
S-phrases	S53, S45, S60, S61
Flash point	Non-flammable
Related compounds
Other anions	Potassium chromate Potassium molybdate Potassium tungstate
Other cations	Ammonium dichromate Sodium dichromate
Related compounds	Potassium permanganate
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references

Potassium dichromate, K₂Cr₂O₇, is a common inorganic chemical reagent, most commonly used as an oxidizing agent in various laboratory and industrial applications. As with all hexavalent chromium compounds, it is potentially harmful to health and must be handled and disposed of appropriately. It is a crystalline ionic solid with a bright, red-orange colour.

Contents 1 Chemistry 2 Uses 2.1 Cleaning 2.2 Construction 2.3 Ethanol determination 2.4 Homeopathic uses 2.5 Leather 2.6 Photography 2.7 Wood treatment 3 Safety 4 Sulfur dioxide 5 References 6 External links

[edit] Chemistry

Potassium dichromate is an oxidizer. The oxidation half-equation can be seen:

Cr₂O₇²⁻(aq) + 14H⁺ + 6e⁻ → 2Cr³⁺(aq) + 7H₂O (E = +1.36 V)

In organic chemistry, potassium dichromate is a mild oxidizer compared with potassium permanganate. It is used to oxidize alcohols. It converts primary alcohols into aldehydes, or into carboxylic acids if heated under reflux. In contrast, with permanganate, carboxylic acids are the sole products. Secondary alcohols are converted into ketones — no further oxidation possible. For example, menthone may be prepared by oxidation of menthol with acidified dichromate.^[1] Tertiary alcohols are not oxidized by potassium dichromate.

In an aqueous solution the colour change exhibited can be used to test whether an aldehyde or ketone is present. When an aldehyde is present the chromium ions will be reduced from the +6 to the +3 oxidation state, changing colour from orange to green. This is because the aldehyde can be further oxidized to the corresponding carboxylic acid. A ketone will show no such change because it cannot be oxidized further, and so the solution will remain orange.

[edit] Uses

[edit] Cleaning

Like other chromium(VI) compounds (chromium trioxide, sodium dichromate), potassium dichromate may be used to prepare "chromic acid", which can be used for cleaning glassware and etching materials.

[edit] Construction

It is used as an ingredient in cement in which it retards the setting of the mixture and improves its density and texture. This usage commonly causes contact dermatitis in construction workers.^[2]

[edit] Ethanol determination

The concentration of ethanol in a sample can be determined by back titration with acidified potassium dichromate. Reacting the sample with an excess of potassium dichromate, all ethanol is oxidized to acetic acid:

C₂H₅OH + [O] → CH₃COOH

The excess dichromate is determined by titration against sodium thiosulfate. Subtracting the amount of excess dichromate from the initial amount, gives the amount of ethanol present. Accuracy can be improved by calibrating the dichromate solution against a blank.

One major application for this reaction is in old police breathalyzer tests. When alcohol vapor makes contact with the yellow dichromate-coated crystals, the color changes from yellow to green. The degree of the color change is directly related to the level of alcohol in the suspect's breath.

[edit] Homeopathic uses

Potassium dichromate is used in the homeopathic preparation of Kali (or Kalium) bichromicum, although little or none remains in the final dilution.^[3] One notable homeopathic product that contains it as the active ingredient is HeadOn,^[4] in which the potassium dichromate is diluted to one part per million.

[edit] Leather

It is used to tan leather which is used for footwear.^[5]

[edit] Photography

Potassium dichromate has important uses in photography and in photographic screen printing, where it is used as an oxidizing agent together with a strong mineral acid.

Gum bichromate printing was one of the very first stable photographic printing processes, dating back to about 1850. A solution of gum arabic and potassium dichromate, once applied to paper and dried, will harden when exposed to ultraviolet light.

Chromium intensification uses potassium dichromate together with equal parts of concentrated hydrochloric acid diluted down to approximately 10% v/v to treat weak and thin negatives of black and white photograph roll. This solution reconverts the elemental silver particles in the film to silver chloride. After thorough washing and exposure to actinic light, the film can be redeveloped to its end-point yielding a stronger negative which is able to produce a more satisfactory print.

A potassium dichromate solution in sulfuric acid can be used to produce a reversal negative (i.e,. a positive transparency from a negative film). This is effected by developing a black and white film but allowing the development to proceed more or less to the end point. The development is then stopped by copious washing and the film then treated in the acid dichromate solution. This converts the silver metal to silver sulfate, a compound that is insensitive to light. After thorough washing and exposure to actinic light, the film is developed again allowing the previously unexposed silver halide to be reduced to silver metal.

The results obtained can be unpredictable, but sometimes excellent results are obtained producing images that would otherwise be unobtainable. This process can be coupled with solarisation so that the end product resembles a negative and is suitable for printing in the normal way.

Cr^VI compounds have the property of tanning animal proteins when exposed to strong light. This quality is used in photographic screen printing. In screen printing a fine screen of bolting silk of similar material that is required to be printed is then taped securely onto the surface of the screen and the whole thing exposed to strong light for a period - typically about half an hour in bright sunlight. When the design is removed, the gelatine on the screen is washed off with hot water. All the gelatine exposed to sun-light will have been hardened by the dichromate and will be retained on the screen leaving a precise mask of the required design which can be printed in the usual way.

[edit] Wood treatment

Potassium dichromate is used to finish certain types of wood. It brings out the color and grain to a very deep, rich appearance. This is particularly effective on mahogany.^[6]

[edit] Safety

Potassium dichromate is one of the most common causes of chromium dermatitis^[7]; chromium is highly likely to induce sensitization leading to dermatitis, especially of the hand and fore-arms, which is chronic and difficult to treat. It is also toxic, with doses of approximately 100 mg/kg being fatal in rabbits and rodents.^[8]

As with other Cr^VI compounds, potassium dichromate is carcinogenic and should be handled with gloves and appropriate health and safety protection. The compound is also corrosive and exposure may produce severe eye damage or blindness.^[9]

[edit] Sulfur dioxide

Potassium dichromate(VI) paper can be used to test for sulfur dioxide, as it turns distinctively from orange to green.

[edit] References

[edit] External links

• International Chemical Safety Card 1371
• National Pollutant Inventory - Chromium VI and compounds fact sheet
• NIOSH Pocket Guide to Chemical Hazards
• European Chemicals Bureau
• IARC Monograph "Chromium and Chromium compounds"