"Glycerine" and "Glycerin" redirect here. For the Bush song, see Glycerine (song).
| Glycerol |
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Other names
glycerin
glycerine
propanetriol
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| Identifiers |
| CAS number |
56-81-5 Y |
| PubChem |
753 |
| ChemSpider |
733 Y |
| UNII |
PDC6A3C0OX Y |
| DrugBank |
DB04077 |
| KEGG |
D00028 Y |
| ChEBI |
CHEBI:17522 Y |
| ChEMBL |
CHEMBL692 Y |
| ATC code |
A06AG04,A06AX01, QA16QA03 |
| Jmol-3D images |
Image 1 |
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InChI=1S/C3H8O3/c4-1-3(6)2-5/h3-6H,1-2H2 Y
Key: PEDCQBHIVMGVHV-UHFFFAOYSA-N Y
InChI=1/C3H8O3/c4-1-3(6)2-5/h3-6H,1-2H2
Key: PEDCQBHIVMGVHV-UHFFFAOYAF
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| Properties |
| Molecular formula |
C3H8O3 |
| Molar mass |
92.09 g mol−1 |
| Appearance |
colorless liquid
hygroscopic |
| Odor |
odorless |
| Density |
1.261 g/cm3 |
| Melting point |
17.8 °C, 291 K, 64 °F
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| Boiling point |
290 °C, 563 K, 554 °F ([2])
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| Refractive index (nD) |
1.4746 |
| Viscosity |
1.412 Pa·s[1] |
| Hazards |
| MSDS |
External MSDS |
| NFPA 704 |
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| Flash point |
160 °C (320 °F) (closed cup)
176 °C (349 °F) (open cup) |
| Supplementary data page |
Structure and
properties |
n, εr, etc. |
Thermodynamic
data |
Phase behaviour
Solid, liquid, gas |
| Spectral data |
UV, IR, NMR, MS |
Y (verify) (what is: Y/N?)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) |
| Infobox references |
Glycerol (or glycerine, glycerin) is a simple polyol compound. It is a colorless, odorless, viscous liquid that is widely used in pharmaceutical formulations. Glycerol has three hydroxyl groups that are responsible for its solubility in water and its hygroscopic nature. The glycerol backbone is central to all lipids known as triglycerides. Glycerol is sweet-tasting and of low toxicity.
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Contents
- 1 Production
- 1.1 From fats and oils
- 1.2 Synthetic glycerol
- 2 Applications
- 2.1 Food industry
- 2.2 Pharmaceutical and personal care applications
- 2.3 Botanical extracts
- 2.4 Antifreeze
- 2.5 Chemical intermediate
- 3 Metabolism
- 4 Historical cases of contamination with diethylene glycol
- 5 See also
- 6 References
- 7 External links
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Production [edit]
Approximately 950,000 tons per annum are produced in the USA and Europe; 350,000 tons of glycerol were produced per year in the United States alone from 2000–2004.[3] Production will increase as the EU directive 2003/30/EC is implemented, which requires the replacement of 5.75% of petroleum fuels with biofuel across all Member States by 2010, as glycerol is a byproduct in the production of biodiesel. It is projected that by the year 2020, production will be six times more than demand.[4]
From fats and oils [edit]
Triglycerides found in fats and oils are by definition esters of glycerol with long-chain carboxylic acids; the hydrolysis (saponification) or transesterification of these triglycerides produces stoichiometric quantities of glycerol. In this scheme, glycerol is produced as a co-product in the production of long-chain carboxylate salts used as soaps (see soap-making):
It is also a byproduct of the production of biodiesel via transesterification. This form of crude glycerin is often dark in appearance with a thick, syrup-like consistency. Triglycerides (1) are treated with an alcohol such as ethanol (2) with catalytic base to give ethyl esters of fatty acids (3) and glycerol (4):
Glycerol from triglycerides is produced on a large scale, but the crude product is of variable quality, with a low selling price of as low as 1–8 U.S. cents per pound in 2011. It can be purified, but the process is expensive. As a result, a good fraction of crude glycerol is disposed of as waste. Some glycerol is burned for energy, but the heat value is low.[5]
Crude glycerol from the hydrolysis of triglycerides can be purified by treatment with activated carbon to remove organic impurities, alkali to remove unreacted glycerol esters, and ion exchange to remove salts. High purity glycerol (> 99.5%) is obtained by multi-step distillation; vacuum is helpful due to the high boiling point of glycerol (290 °C).[4]
Synthetic glycerol [edit]
Synthetic glycerol refers to material obtained from non-triglyceride sources. Glycerol may also be produced by various routes from propylene. The epichlorohydrin process is the most important; it involves the chlorination of propylene to give allyl chloride, which is oxidized with hypochlorite to dichlorohydrins, which reacts with a strong base to give epichlorohydrin. Epichlorohydrin is then hydrolyzed to give glycerol. Chlorine-free processes from propylene include the synthesis of glycerol from acrolein and propylene oxide.[4]
Because of the emphasis on biodiesel, where glycerol is a waste product, the market for glycerol is depressed, and these old processes are no longer economical on a large scale. Due to the glycerol glut, efforts are being made to convert glycerol to its precursors, such as acrolein and epichlorohydrin (see #Chemical intermediate).
Applications [edit]
Food industry [edit]
In foods and beverages, glycerol serves as a humectant, solvent, and sweetener, and may help preserve foods. It is also used as filler in commercially prepared low-fat foods (e.g., cookies), and as a thickening agent in liqueurs. Glycerol and water are used to preserve certain types of leaves.[6] As a sugar substitute, it has approximately 27 kilocalories per teaspoon (sugar has 20) and is 60% as sweet as sucrose. It does not feed the bacteria that form plaques and cause dental cavities. As a food additive, glycerol is labeled as E number E422. It is added to icing (frosting) to prevent it setting too hard.
As used in foods, glycerol is categorized by the American Dietetic Association as a carbohydrate. The U.S. Food and Drug Administration (FDA) carbohydrate designation includes all caloric macronutrients excluding protein and fat. Glycerol has a caloric density similar to table sugar, but a lower glycemic index and different metabolic pathway within the body, so some dietary advocates accept glycerol as a sweetener compatible with low carbohydrate diets.
Pharmaceutical and personal care applications [edit]
Glycerol suppositories used as laxatives
Glycerol is used in medical and pharmaceutical and personal care preparations, mainly as a means of improving smoothness, providing lubrication and as a humectant. It is found in allergen immunotherapies, cough syrups, elixirs and expectorants, toothpaste, mouthwashes, skin care products, shaving cream, hair care products, soaps and water-based personal lubricants. In solid dosage forms like tablets, glycerol is used as a tablet holding agent. For human consumption, glycerol is classified by the U.S. FDA among the sugar alcohols as a caloric macronutrient.
Glycerol is a component of glycerin soap. Essential oils are added for fragrance. This kind of soap is used by people with sensitive, easily-irritated skin because it prevents skin dryness with its moisturizing properties. It draws moisture up through skin layers and slows or prevents excessive drying and evaporation.[citation needed] With similar benefits, glycerin is a common ingredient in many bath salts recipes. However, some assert that due to glycerin's moisture absorbing properties, it can be more of a hindrance than a benefit.[7]
Glycerol can be used as a laxative when introduced into the rectum in suppository or small-volume (2–10 ml) (enema) form; it irritates the anal mucosa and induces a hyperosmotic effect.[8]
Taken orally (often mixed with fruit juice to reduce its sweet taste), glycerol can cause a rapid, temporary decrease in the internal pressure of the eye. This can be a useful initial emergency treatment of severely elevated eye pressure.[9]
[edit]
When utilized in 'tincture' method extractions, specifically as a 10% solution, glycerol prevents tannins from precipitating in ethanol extracts of plants (tinctures). It is also used as an 'alcohol-free' alternative to ethanol as a solvent in preparing herbal extractions. It is less extractive when utilized in a standard tincture methodology. Glycerol is approximately 30% more slowly absorbed by the body resulting in a much lower glycemic load. Alcohol-based tinctures can also have the alcohol removed and replaced with glycerol for its preserving properties. Such products are not 'alcohol-free' in either a scientific or consumable sense, but should in all instances more accurately be referred to as "Alcohol-Removed" products. Fluid extract manufacturers often extract herbs in hot water before adding glycerin to make glycerites.[10][11]
When used as a primary 'true' alcohol-free (e.g. no alcohol (i.e. ethanol) ever being used) botanical extraction solvent in innovative non-tincture based 'dynamic' methodologies, glycerol has been shown to possess a high degree of extractive versatility for botanicals including removal of numerous constituents and complex compounds, with an extractive power that can rival that of alcohol and water/alcohol solutions. That glycerol possess such high extractive power assumes that glycerol, with its tri-atomic structure, is utilized with dynamic methodologies as opposed to standard passive 'tincturing' methodologies that are better suited to alcohol's di-atomic structure. Glycerol possesses the intrinsic property of not denaturing or rendering a botanical's constituents inert (as di-atomic alcohols – i.e. ethanolic (grain) alcohol, methanolic (wood) alcohol, etc., do). Glycerol is a stable preserving agent for botanical extracts that, when utilized in proper concentrations in an extraction solvent base, does not allow inverting or reduction-oxidation of a finished extract's constituents, even over several years. Both glycerol and ethanol are viable preserving agents. Glycerol is bacteriostatic in its action, and ethanol is bactericidal in its action.[12][13][14]
Antifreeze [edit]
Main article: antifreeze
Like ethylene glycol and propylene glycol, glycerol is a non-ionic kosmotrope that forms strong hydrogen bonds with water molecules, competing with water-water hydrogen bonds. This disrupts the crystal lattice formation of ice unless the temperature is significantly lowered. The minimum freezing point temperature is at about −36 °F / −37.8 °C corresponding to 70% glycerol in water.
Glycerol was historically used as an anti-freeze for automotive applications before being replaced by ethylene glycol, which has a lower freezing point. While the minimum freezing point of a glycerol-water mixture is higher than an ethylene glycol-water mixture, glycerol is not toxic and is being re-examined for use in automotive applications.[15][16]
In the laboratory, glycerol is a common component of solvents for enzymatic reagents stored at temperatures below 0 °C due to the depression of the freezing temperature. It is also used as a cryoprotectant where the glycerol is dissolved in water to reduce damage by ice crystals to laboratory organisms that are stored in frozen solutions, such as bacteria, nematodes, and mammalian embryos.
Chemical intermediate [edit]
Glycerol is used to produce nitroglycerin, which is an essential ingredient of various explosives such as dynamite, gelignite, and propellants like cordite. Reliance on soap-making to supply co-product glycerine made it difficult to increase production to meet wartime demand. Hence, synthetic glycerin processes were national defense priorities in the days leading up to World War II. Nitroglycerin, also known as glyceryl trinitrate (GTN) is commonly used to relieve angina pectoris, taken in the form of sub-lingual tablets, or as an aerosol spray.
A great deal of research is being conducted to try to make value-added products from crude glycerol (typically containing 20% water and residual esterification catalyst) obtained from biodiesel production.[17] The use of crude glycerin as an additive to biomass for a renewable energy source when burned or gasified is also being explored.
- Hydrogen gas production unit[18]
- Glycerine acetate (as a potential fuel additive)[19]
- Conversion to propylene glycol[20]
- Conversion to acrolein[21][22]
- Conversion to ethanol[23]
- Conversion to epichlorohydrin,[24] a raw material for epoxy resins
Metabolism [edit]
Glycerol is a precursor for synthesis of triacylglycerols and of phospholipids in the liver and adipose tissue. When the body uses stored fat as a source of energy, glycerol and fatty acids are released into the bloodstream. In some organisms, the glycerol component can be converted into glucose by the liver and, thus, provide energy for cellular metabolism.
Before glycerol can enter the pathway of glycolysis or gluconeogenesis (depending on physiological conditions), it must be converted to their intermediate glyceraldehyde 3-phosphate in the following steps:
| Glycerol |
Glycerol kinase |
Glycerol-3-phosphate |
Glycerol-3-phosphate dehydrogenase |
Dihydroxyacetone phosphate |
Triosephosphate isomerase |
Glyceraldehyde 3-phosphate |
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ATP |
ADP |
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NAD+ |
NADH
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NAD+ |
NADH
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The enzyme glycerol kinase is present only in the liver. In adipose tissue, glycerol 3-phosphate is obtained from dihydroxyacetone phosphate (DHAP) with the enzyme glycerol-3-phosphate dehydrogenase.
Glycerol has very low toxicity when ingested; its LD50 oral dose for rats is 12600 mg/kg and 8700 mg/kg for mice.[25]
Historical cases of contamination with diethylene glycol [edit]
Glycerol and diethylene glycol are similar in appearance, smell, and taste. The US Federal Food, Drug, and Cosmetic Act was passed following the 1937 "Elixir sulfanilamide" incident of poisoning caused by diethylene glycol contamination of medicine.
On May 4, 2007, the US Food and Drug Administration advised all US makers of medicines to test all batches of glycerol for the toxic diethylene glycol.[26] This followed an occurrence of hundreds of fatal poisonings in Panama resulting from a Chinese factory deliberately falsifying records in order to export the cheaper diethylene glycol as the more expensive glycerol.[27]
See also [edit]
- Epichlorohydrin
- Nitroglycerin
- Oleochemicals
- Saponification/Soap making
- Solketal
- Sugar alcohol
- Transesterification
References [edit]
- ^ "Viscosity of Glycerol and its Aqueous Solutions". Retrieved 2011-04-19.
- ^ Lide, D. R., ed. (1994). CRC Handbook of Data on Organic Compounds (3rd ed.). Boca Raton, FL: CRC Press. p. 4386.
- ^ Nilles, Dave (2005). "A Glycerin Factor". Biodiesel Magazine.
- ^ a b c Christoph, Ralf; Schmidt, Bernd; Steinberner, Udo; Dilla, Wolfgang; Karinen, Reetta (2006). Glycerol. "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a12_477.pub2. ISBN 3527306730.
- ^ Bryan Sims (2011-10-25). "Clearing the Way for Byproduct Quality: Why quality for glycerin is just as important for biodiesel". Biodiesel Magazine.
- ^ Stevens, Alan. "Preserving flowers and decorative foliages with glycerin and dye".
- ^ "Glycerin in Bath Salts – Health Benefits for the Skin". Homemade Bath Salts Recipes. Retrieved 22 February 2013.
- ^ "Glycerin Enema". Drugs.com. Retrieved 2012-11-17.
- ^ "Glycerin (Oral Route)". Mayo Foundation for Medical Education and Research. Retrieved 2012-11-17.
- ^ Long, Walter S. (Jan. 14, 1916 – Jan. 13, 1917). "The Composition of Commercial Fruit Extracts". Transactions of the Kansas Academy of Science 28: 157–161. doi:10.2307/3624347. JSTOR 3624347.
- ^ Does Alcohol Belong In Herbal Tinctures? newhope.com
- ^ GLYCEROL AND THE GLYCOLS – Production, Properties and Analysis by, James W. Lawrie, Ph.D. (1928 The Chemical Catalog Company, Inc., New York, NY).
- ^ GLYCERIN – Its Industrial and Commercial Applications, by Georgia Leffingwell, Ph.D. and Miton Lesser, B.S. (1945 Chemical Publishing Co., Inc., Brooklyn, NY).
- ^ The Manufacture of GLYCEROL – Vol. III (1956 The Technical Press, LTD., London, UK).
- ^ Hudgens, R. Douglas; Hercamp, Richard D.; Francis, Jaime; Nyman, Dan A.; Bartoli, Yolanda (2007). An Evaluation of Glycerin (Glycerol) as a Heavy Duty Engine Antifreeze/Coolant Base. doi:10.4271/2007-01-4000.
- ^ Proposed ASTM Engine Coolant Standards Focus on Glycerin. Astmnewsroom.org. Retrieved on 2012-08-15.
- ^ Johnson, Duane T.; Taconi, Katherine A. (2007). "The glycerin glut: Options for the value-added conversion of crude glycerol resulting from biodiesel production". Environmental Progress 26 (4): 338. doi:10.1002/ep.10225.
- ^ Marshall, A. T. and Haverkamp, R. G. (2008). "Production of hydrogen by the electrochemical reforming of glycerol-water solutions in a PEM electrolysis cell". International Journal of Hydrogen Energy 33 (17): 4649–4654. doi:10.1016/j.ijhydene.2008.05.029.
- ^ Melero, Juan A.; Van Grieken, Rafael; Morales, Gabriel; Paniagua, Marta (2007). "Acidic mesoporous silica for the acetylation of glycerol: Synthesis of bioadditives to petrol fuel". Energy Fuels 21 (3): 1782–1791. doi:10.1021/ef060647q.
- ^ "Dow achieves another major milestone in its quest for sustainable chemistries" (Press release). Dow Chemical Company. 2007-03-15.
- ^ Ott, L.; Bicker, M.; Vogel, H. (2006). "The catalytic dehydration of glycerol in sub- and supercritical water: a new chemical process for acrolein production". Green Chemistry 8 (2): 214–220. doi:10.1039/b506285c.
- ^ Watanabe, Masaru; Iida, Toru; Aizawa, Yuichi; Aida, Taku M.; Inomata, Hiroshi (2007). "Acrolein synthesis from glycerol in hot-compressed water". Bioresource Technology 98 (6): 1285–1290. doi:10.1016/j.biortech.2006.05.007. PMID 16797980.
- ^ Yazdani, S. S. and Gonzalez, R. (2007). "Anaerobic fermentation of glycerol: a path to economic viability for the biofuels industry". Current Opinion in Biotechnology 18 (3): 213–219. doi:10.1016/j.copbio.2007.05.002. PMID 17532205. Lay summary – ScienceDaily (27 Jun 2007).
- ^ "Dow Epoxy advances glycerine-to-epichlorohydrin and liquid epoxy resins projects by choosing Shanghai site" (Press release). Dow Chemical Company. 26 March 2007.
- ^ Safety data for glycerol http://msds.chem.ox.ac.uk/GL/glycerol.html
- ^ "FDA Advises Manufacturers to Test Glycerin for Possible Contamination". U.S. Food and Drug Administration. May 4, 2007. Retrieved May 8, 2007.
- ^ Walt Bogdanich (2007-05-06). "From China to Panama, a Trail of Poisoned Medicine". New York Times. Retrieved May 8, 2007.
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Sugar alcohols
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| 1-carbon |
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| 2-carbon |
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| 3-carbon |
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| 4-carbon |
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| 5-carbon |
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| 6-carbon |
- Mannitol
- Sorbitol
- Galactitol
- Iditol
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| 7-carbon |
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| Deoxy sugar alcohols |
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| Cyclic sugar alcohols |
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| Glycylglycitols |
- Maltitol
- Lactitol
- Isomalt
- Maltotriitol
- Maltotetraitol
- Polyglycitol
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External links [edit]
- CDC - NIOSH Pocket Guide to Chemical Hazards - Glycerin (mist)
