Bleach

A bleach is a chemical that removes color or whitens, often via oxidation. Common chemical bleaches include household "chlorine bleach", a solution of approximately 3-6% sodium hypochlorite (NaOCl), and "oxygen bleach", which contains hydrogen peroxide or a peroxide-releasing compound such as sodium perborate or sodium percarbonate. To bleach something is to apply bleach, sometimes as a preliminary step in the process of dyeing. Bleaching powder is calcium hypochlorite.

Other types of bleaches

Chlorine dioxide is used for the bleaching of wood pulp, fats and oils, cellulose, flour, textiles, beeswax, skin, and in a number of other industries.

In the food industry, some organic peroxides (benzoyl peroxide, etc.) and other agents (e.g. bromates) are used as flour bleaching and maturing agents.

Peracetic acid, ozone and hydrogen peroxide and oxygen are used in bleaching sequences in the pulp industry to produce totally chlorine free (TCF) paper.

Not all bleaches are hazardous and have a oxidizing nature. Sodium dithionite is used as a powerful reducing agent in some bleaching formulas. It is commonly used to bleach wood pulp used to make newsprint.

Hazards

Since bleaches are strong oxidizing agents, they can be quite hazardous, especially when reacted with other common household chemicals.

Mixing sodium hypochlorite with acids like vinegar, drain cleaners containing sodium bisulfate (sodium hydrogen sulfate), or even lemon juice can release chlorine. Hypochlorite and chlorine are in equilibrium in water; the position of the equilibrium is pH dependent and low pH (acidic) favors chlorine,^[1]

Cl₂ + H₂O $\rightleftharpoons$ H⁺ + Cl^- + HClO

Chlorine is a respiratory irritant that attacks mucous membranes and burns the skin. As little as 3.5 ppm can be detected as an odor, and 1000 ppm is likely to be fatal after a few deep breaths. Exposure to chlorine has been limited to 0.5 ppm (8-hour time-weighted average—40 hour week) by OSHA in the U.S.^[2]

Sodium hypochlorite and ammonia react to form a number of products, depending on the temperature, concentration, and how they are mixed. ^[3]. The main reaction is chlorination of ammonia, first giving chloramine (NH₂Cl), then NHCl₂ and finally nitrogen trichloride (NCl₃). These materials are very irritating to eyes and lungs and are toxic above certain concentrations.

NH₃ + NaOCl --> NaOH + NH₂Cl

NH₂Cl + NaOCl --> NaOH + NHCl₂

NHCl₂ + NaOCl --> NaOH + NCl₃

Additional reactions produce hydrazine, in a variation of the Olin Raschig process.

NH₃ + NH₂Cl + NaOH --> N₂H₄ + NaCl + H₂O

The hydrazine generated can further react with the monochloramine in an exothermic reaction:^[1]

2 NH₂Cl + N₂H₄ --> 2 NH₄Cl + N₂

Industrial bleaching agents can also be sources of concern. For example, the use of elemental chlorine in the bleaching of wood pulp produces organochlorines, persistent organic pollutants, including dioxins. According to an industry group, the use of chlorine dioxide in these processes has reduced the dioxin generation to under detectable levels.^[4] However, respiratory risk from chlorine and highly toxic chlorinated byproducts still

A recent study ^[5]indicated for the first time that sodium hypochlorite and organic chemicals (e.g., surfactants, fragrances) contained in several household cleaning products react to generate chlorinated volatile organic compounds (VOCs). These chlorinated compounds are emitted during cleaning applications and most of them are toxic and probable human carcinogens. The study showed that indoor air concentrations significantly increase (8-52 times for chloroform and 1-1170 times for carbon tetrachloride) during the use of bleach containing products. The increase in chlorinated volatile organic compound concentrations was the lowest for plain bleach and the highest for the products in the form of “thick liquid and gel”. The significant increases observed in indoor air concentrations of several chlorinated VOCs (especially carbon tetrachloride and chloroform) indicate that the bleach use is a newly identified source that could be important in terms of inhalation exposure to these compounds. Preliminary risk assessment suggested that using these cleaning products may significantly increase the cancer risk ^[6]. Further studies are also needed for a detailed investigation of the health risks associated with the use of these products and other possible exposure routes (i.e., dermal). However, these are not the only adverse environmental effects of the released VOCs, they are also ozone depleting compounds and powerful greenhouse gases.

Chemistry

The process of bleaching can be summarised in the following set of chemical reaction:

Cl₂(aq) + H₂O(l) $\rightleftharpoons$ H⁺(aq) + Cl^-(aq) + HClO(aq)

The H⁺ ion of the hypochlorous acid then dissolves into solution, and so the final result is effectively:

Cl₂(aq) + H₂O(l) $\rightleftharpoons$ 2H⁺(aq) + Cl^-(aq) + ClO^-(aq)

Mechanism of bleach action

Color in most dyes and pigments is produced by molecules, such as beta carotene, which contain chromophores. Chemical bleaches work in one of two ways:

An oxidizing bleach works by breaking the chemical bonds that make up the chromophore. This changes the molecule into a different substance that either does not contain a chromophore, or contains a chromophore that does not absorb visible light.

A reducing bleach works by converting double bonds in the chromophore into single bonds. This eliminates the ability of the chromophore to absorb visible light.^[7]

Sunlight acts as a bleach through a process leading to similar results: high energy photons of light, often in the violet or ultraviolet range, can disrupt the bonds in the chromophore, rendering the resulting substance colorless. Extended exposure often leads to massive discoloration usually reducing the colors to white and typically very faded blue spectrums.^[8]

References

^ ^a ^b Cotton, F.A (1972). Advanced Inorganic Chemistry. John Wiley and Sons Inc. ISBN 0-471-17560-9. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)
^ Occupational Safety & Health Administration (2007). and peroxide/recognition.html "OSHA -- Chlorine". OSHA. Retrieved 2007-08-26. {{cite web}}: Check |url= value (help)
^ Rizk-Ouaini, Rosette; Ferriol, Michel; Gazet, Josette; Saugier-Cohen Adad, Marie Therese (1986), "Oxidation reaction of ammonia with sodium hypochlorite. Production and degradation reactions of chloramines.", Bulletin de la Societe Chimique de France, 4: 512–21{{citation}}: CS1 maint: multiple names: authors list (link)
^ "ECF: The Sustainable Technology" (PDF). Alliance for Environmental Technology. Retrieved 2007-09-19. {{cite web}}: Cite has empty unknown parameter: |coauthors= (help)
^ Odabasi, M., “Halogenated Volatile Organic Compounds from the Use of Chlorine-Bleach- Containing Household Products”, Environmental Science & Technology 42, 1445-1451, (2008). Available at: http://pubs.acs.org/journals/esthag/
^ Odabasi, M., “Halogenated Volatile Organic Compounds from the Use of Chlorine-Bleach- Containing Household Products, Slide presentation (2008). Available at: http://www.slideworld.org/ViewSlides.aspx?URL=5092
^ Field, Simon Q (2006). "Ingredients -- Bleach". Science Toys. Retrieved 2006-03-02.
^ Bloomfield, Louis A (2006). "Sunlight". How Things Work Home Page. Retrieved 2006-03-02.

External links

American Chemistry Council, Chlorine Chemistry Division

[c&w-1] Cotton, F.A (1972). Advanced Inorganic Chemistry. John Wiley and Sons Inc. ISBN 0-471-17560-9. {{cite book}}: Unknown parameter |coauthors= ignored (|author= suggested) (help)

[2] Occupational Safety & Health Administration (2007). and peroxide/recognition.html "OSHA -- Chlorine". OSHA. Retrieved 2007-08-26. {{cite web}}: Check |url= value (help)

[3] Rizk-Ouaini, Rosette; Ferriol, Michel; Gazet, Josette; Saugier-Cohen Adad, Marie Therese (1986), "Oxidation reaction of ammonia with sodium hypochlorite. Production and degradation reactions of chloramines.", Bulletin de la Societe Chimique de France, 4: 512–21{{citation}}: CS1 maint: multiple names: authors list (link)

[4] "ECF: The Sustainable Technology" (PDF). Alliance for Environmental Technology. Retrieved 2007-09-19. {{cite web}}: Cite has empty unknown parameter: |coauthors= (help)

[5] Odabasi, M., “Halogenated Volatile Organic Compounds from the Use of Chlorine-Bleach- Containing Household Products”, Environmental Science & Technology 42, 1445-1451, (2008). Available at: http://pubs.acs.org/journals/esthag/

[6] Odabasi, M., “Halogenated Volatile Organic Compounds from the Use of Chlorine-Bleach- Containing Household Products, Slide presentation (2008). Available at: http://www.slideworld.org/ViewSlides.aspx?URL=5092

[7] Field, Simon Q (2006). "Ingredients -- Bleach". Science Toys. Retrieved 2006-03-02.

[8] Bloomfield, Louis A (2006). "Sunlight". How Things Work Home Page. Retrieved 2006-03-02.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]