Tributyl phosphate

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Tributyl phosphate
Tributyl phosphate Structural Formula V1.svg
Spacefill model of Tributyl phosphate Tributyl-phosphate-3D-vdW.png
Spacefill model of Tributyl phosphate
Ball and stick model of Tributyl phosphate Tributyl phosphate-3D-balls-by-AHRLS-2012.png
Ball and stick model of Tributyl phosphate
Names
Preferred IUPAC name
Tributyl phosphate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.004.365 OOjs UI icon edit-ltr-progressive.svg
KEGG
PubChem CID
UNII
  • InChI=1S/C12H27O4P/c1-4-7-10-14-17(13,15-11-8-5-2)16-12-9-6-3/h4-12H2,1-3H3 Yes check.svgY
    Key: STCOOQWBFONSKY-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C12H27O4P/c1-4-7-10-14-17(13,15-11-8-5-2)16-12-9-6-3/h4-12H2,1-3H3
    Key: STCOOQWBFONSKY-UHFFFAOYAN
  • O=P(OCCCC)(OCCCC)OCCCC
Properties
C12H27O4P
Molar mass 266.318 g·mol−1
AppearanceColorless to pale-yellow liquid [1]
Density 0.9727 g/mL
Melting point −80 °C (−112 °F; 193 K)
Boiling point 289 °C (552 °F; 562 K)
0.4 g/L [2]
Vapor pressure 0.004 mmHg (25°C) [1]
1.4231 (at 20 °C) [3]
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
1
1
Flash point 146.1 °C (295.0 °F; 419.2 K)
Lethal dose or concentration (LD, LC):
1189 mg/kg (mouse, oral)
3000 mg/kg (rat, oral) [4]
227 ppm (cat, 4–5 h)
123 ppm (rat, 6 h)
117 ppm (rat)
2529 ppm (rat, 1 h) [4]
2214 ppm (cat, 5 h) [4]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 5 mg/m3 [1]
REL (Recommended)
TWA 0.2 ppm (2.5 mg/m3) [1]
IDLH (Immediate danger)
30 ppm [1]
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Tributyl phosphate, known commonly as TBP, is an organophosphorus compound with the chemical formula (CH3CH2CH2CH2O)3PO. This colourless, odorless liquid finds some applications as an extractant and a plasticizer. It is an ester of phosphoric acid with n-butanol.

Contents

Production

Tributyl phosphate is manufactured by reaction of phosphoryl chloride with n-butanol. [5]

POCl3 + 3 C4H9OH → PO(OC4H9)3 + 3 HCl

Production is estimated at 3,000–5,000 tonnes worldwide. [6]

Use

TBP is a solvent and plasticizer for cellulose esters such as nitrocellulose and cellulose acetate. It is also used as a flame retardant for cellulose fabrics such as cotton. [7] [8] It forms stable hydrophobic complexes with some metals; these complexes are soluble in organic solvents as well as supercritical CO2. The major uses of TBP in industry are as a component of aircraft hydraulic fluid, brake fluid, and as a solvent for extraction and purification of rare-earth metals from their ores. [6]

TBP finds its use as a solvent in inks, synthetic resins, gums, adhesives (namely for veneer plywood), and herbicide and fungicide concentrates.

As it has no odour, it is used as an anti-foaming agent in detergent solutions, and in various emulsions, paints, and adhesives. It is also found as a de-foamer in ethylene glycol-borax antifreeze solutions.[ citation needed ] In oil-based lubricants addition of TBP increases the oil film strength. It is used also in mercerizing liquids, where it improves their wetting properties. It can be used as a heat-exchange medium. [9] TBP is used in some consumer products such as herbicides and water-thinned paints and tinting bases. [10]

Nuclear chemistry

Tributyl phosphate is used in combination with di(2-ethylhexyl)phosphoric acid for the solvent extraction of uranium, as part of the purification of natural ores. [11] It is also used in nuclear reprocessing as part of the PUREX process. A 15–40% (usually about 30%) solution of tributyl phosphate in kerosene or dodecane is used in the liquid–liquid extraction (solvent extraction) of uranium, plutonium, and thorium from spent uranium nuclear fuel rods dissolved in nitric acid.

Hazards

In contact with concentrated nitric acid the TBP-kerosene solution forms hazardous and explosive red oil.

Related Research Articles

<span class="mw-page-title-main">Nuclear reprocessing</span> Chemical operations that separate fissile material from spent fuel to be recycled as new fuel

Nuclear reprocessing is the chemical separation of fission products and actinides from spent nuclear fuel. Originally, reprocessing was used solely to extract plutonium for producing nuclear weapons. With commercialization of nuclear power, the reprocessed plutonium was recycled back into MOX nuclear fuel for thermal reactors. The reprocessed uranium, also known as the spent fuel material, can in principle also be re-used as fuel, but that is only economical when uranium supply is low and prices are high. Nuclear reprocessing may extend beyond fuel and include the reprocessing of other nuclear reactor material, such as Zircaloy cladding.

<span class="mw-page-title-main">Nuclear chemistry</span> Branch of chemistry dealing with radioactivity, transmutation and other nuclear processes

Nuclear chemistry is the sub-field of chemistry dealing with radioactivity, nuclear processes, and transformations in the nuclei of atoms, such as nuclear transmutation and nuclear properties.

Dodecane (also known as dihexyl, bihexyl, adakane 12, or duodecane) is an oily liquid n-alkane hydrocarbon with the chemical formula C12H26 (which has 355 isomers).

<span class="mw-page-title-main">Ion exchange</span> Exchange of ions between an electrolyte solution and a solid

Ion exchange is a reversible interchange of one kind of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid with the reaction being used especially for softening or making water demineralised, the purification of chemicals and separation of substances.

<span class="mw-page-title-main">Phosphorus trichloride</span> Chemical compound

Phosphorus trichloride is an inorganic compound with the chemical formula PCl3. A colorless liquid when pure, it is an important industrial chemical, being used for the manufacture of phosphites and other organophosphorus compounds. It is toxic and reacts readily with water to release hydrogen chloride.

<span class="mw-page-title-main">PUREX</span> Spent fuel reprocessing process for plutonium and uranium recovery

PUREX is a chemical method used to purify fuel for nuclear reactors or nuclear weapons. PUREX is the de facto standard aqueous nuclear reprocessing method for the recovery of uranium and plutonium from used nuclear fuel. It is based on liquid–liquid extraction ion-exchange.

<span class="mw-page-title-main">Thermal Oxide Reprocessing Plant</span> Waived nuclear fuel reprocessing plant in England, UK

The Thermal Oxide Reprocessing Plant, or THORP, is a nuclear fuel reprocessing plant at Sellafield in Cumbria, England. THORP is owned by the Nuclear Decommissioning Authority and operated by Sellafield Ltd.

Liquid–liquid extraction (LLE), also known as solvent extraction and partitioning, is a method to separate compounds or metal complexes, based on their relative solubilities in two different immiscible liquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer of one or more species from one liquid into another liquid phase, generally from aqueous to organic. The transfer is driven by chemical potential, i.e. once the transfer is complete, the overall system of chemical components that make up the solutes and the solvents are in a more stable configuration. The solvent that is enriched in solute(s) is called extract. The feed solution that is depleted in solute(s) is called the raffinate. LLE is a basic technique in chemical laboratories, where it is performed using a variety of apparatus, from separatory funnels to countercurrent distribution equipment called as mixer settlers. This type of process is commonly performed after a chemical reaction as part of the work-up, often including an acidic work-up.

<span class="mw-page-title-main">Phosphoryl chloride</span> Chemical compound

Phosphoryl chloride is a colourless liquid with the formula POCl3. It hydrolyses in moist air releasing phosphoric acid and fumes of hydrogen chloride. It is manufactured industrially on a large scale from phosphorus trichloride and oxygen or phosphorus pentoxide. It is mainly used to make phosphate esters such as tricresyl phosphate.

<span class="mw-page-title-main">Triethyl phosphate</span> Chemical compound

Triethyl phosphate is an organic chemical compound with the formula (C2H5)3PO4 or OP(OEt)3. It is a colorless liquid. It is the triester of ethanol and phosphoric acid and can be called "phosphoric acid, triethyl ester".

Pulsed columns are a type of liquid-liquid extraction equipment; examples of this class of extraction equipment is used at the BNFL plant THORP.

<span class="mw-page-title-main">Magnox Reprocessing Plant</span> Nuclear reprocessing plant at Sellafield

The Magnox Reprocessing Plant is a former nuclear reprocessing facility at Sellafield in northern England, which operated from 1964 to 2022. The plant used PUREX chemistry to extract plutonium and uranium from used nuclear fuel originating primarily from Magnox reactors. The plant was originally constructed and operated by the United Kingdom Atomic Energy Authority (UKAEA), but in 1971 control was transferred to British Nuclear Fuels Limited (BNFL). Since 2005 the plant has been operated by Sellafield Ltd.

<span class="mw-page-title-main">Uranyl</span> Oxycation of uranium

The uranyl ion is an oxycation of uranium in the oxidation state +6, with the chemical formula UO2+
2
. It has a linear structure with short U–O bonds, indicative of the presence of multiple bonds between uranium and oxygen. Four or more ligands may be bound to the uranyl ion in an equatorial plane around the uranium atom. The uranyl ion forms many complexes, particularly with ligands that have oxygen donor atoms. Complexes of the uranyl ion are important in the extraction of uranium from its ores and in nuclear fuel reprocessing.

<span class="mw-page-title-main">Ammonium polyphosphate</span> Chemical compound

Ammonium polyphosphate is an inorganic salt of polyphosphoric acid and ammonia containing both chains and possibly branching. Its chemical formula is H(NH4PO3)nOH showing that each monomer consists of an orthophosphate radical of a phosphorus atom with three oxygens and one negative charge neutralized by an ammonium cation leaving two bonds free to polymerize. In the branched cases some monomers are missing the ammonium anion and instead link to three other monomers.

Heavy Water Board (HWB) is a constituent unit under the Department of Atomic Energy in the Government of India. The organisation is primarily responsible for production of heavy water (D2O) which is used as a moderator and coolant in nuclear power as well as research reactors. Other than heavy water, the HWB is also engaged with production of nuclear grade solvents and extraction of rare materials. India is one of the largest manufacturers of heavy water in the world. Similarly, India has one of the world's largest fleets of pressurized heavy water reactors producing most of India's nuclear power supply.

<span class="mw-page-title-main">Bismuth phosphate process</span>

The bismuth-phosphate process was used to extract plutonium from irradiated uranium taken from nuclear reactors. It was developed during World War II by Stanley G. Thompson, a chemist working for the Manhattan Project at the University of California, Berkeley. This process was used to produce plutonium at the Hanford Site. Plutonium was used in the atomic bomb that was used in the atomic bombing of Nagasaki in August 1945. The process was superseded in the 1950s by the REDOX and PUREX processes.

<span class="mw-page-title-main">BTBP</span> A class of tetradentate ligand compounds

The bis-triazinyl bipyridines (BTBPs) are a class of chemical compounds which are tetradentate ligands similar in shape to quaterpyridine. The BTBPs are made by the reaction of hydrazine and a 1,2-diketone with 6,6'-dicyano-2,2'-bipyridine. The dicyanobipy can be made by reacting 2,2'-bipy with hydrogen peroxide in acetic acid, to form 2,2'-bipyridine-N,N-dioxide. The 2,2'-bipyridine-N,N-dioxide is then converted into the dicyano compound by treatment with potassium cyanide and benzoyl chloride in a mixture of water and THF.

<span class="mw-page-title-main">Di(2-ethylhexyl)phosphoric acid</span> Chemical compound

Di(2-ethylhexyl)phosphoric acid (DEHPA or HDEHP) is an organophosphorus compound with the formula (C8H17O)2PO2H. The colorless liquid is a diester of phosphoric acid and 2-ethylhexanol. It is used in the solvent extraction of uranium, vanadium and the rare-earth metals.

<span class="mw-page-title-main">Actinide chemistry</span> Branch of nuclear chemistry

Actinide chemistry is one of the main branches of nuclear chemistry that investigates the processes and molecular systems of the actinides. The actinides derive their name from the group 3 element actinium. The informal chemical symbol An is used in general discussions of actinide chemistry to refer to any actinide. All but one of the actinides are f-block elements, corresponding to the filling of the 5f electron shell; lawrencium, a d-block element, is also generally considered an actinide. In comparison with the lanthanides, also mostly f-block elements, the actinides show much more variable valence. The actinide series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium.

The advanced reprocessing of spent nuclear fuel is a potential key to achieve a sustainable nuclear fuel cycle and to tackle the heavy burden of nuclear waste management. In particular, the development of such advanced reprocessing systems may save natural resources, reduce waste inventory and enhance the public acceptance of nuclear energy. This strategy relies on the recycling of major actinides and the transmutation of minor actinides in appropriate reactors. In order to fulfill this objective, selective extracting agents need to be designed and developed by investigating their complexation mechanism.

References

  1. 1 2 3 4 5 NIOSH Pocket Guide to Chemical Hazards. "#0625". National Institute for Occupational Safety and Health (NIOSH).
  2. Velavendan, P; Sachithanantham, Ganesh; Pandey, N.K.; Geetha, R; Ahmed, M; Mudali, Kamachi; Natarajan, Rajamani (2012). "Studies on solubility of TBP in aqueous solutions of fuel reprocessing". Journal of Radioanalytical and Nuclear Chemistry. 295 (2): 1113–1117. doi:10.1007/s10967-012-1945-1. S2CID   95976379.
  3. Pabst, Florian; Blochowicz, Thomas (December 2022). "On the intensity of light scattered by molecular liquids - Comparison of experiment and quantum chemical calculations". The Journal of Chemical Physics . 157 (24): 244501. Bibcode:2022JChPh.157x4501P. doi: 10.1063/5.0133511 . PMID   36586992.
  4. 1 2 3 "Tributyl phosphate". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  5. G. R. Dutton and C. R. Noller (1943). "n-Butyl phosphate". Organic Syntheses .; Collective Volume, vol. 2, p. 109
  6. 1 2 "Tributyl Phosphate | SIDS Initial Assessment Profile" (PDF). Japan Chemical Industry Ecology-Toxicology & Information Center. Archived from the original (PDF) on 2007-10-11.
  7. Alongi, Jenny; Malucelli, Giulio (2015). "Cotton flame retardancy: state of the art and future perspectives". RSC Advances. 5 (31): 24239–24263. Bibcode:2015RSCAd...524239A. doi:10.1039/C5RA01176K.
  8. Gaan, Sabyasachi; Sun, Gang (June 2007). "Effect of phosphorus flame retardants on thermo-oxidative decomposition of cotton". Polymer Degradation and Stability. 92 (6): 968–974. doi:10.1016/j.polymdegradstab.2007.03.009.
  9. "Tributyl Phosphate Product Information". Great Vista Chemicals. 20 January 2023.
  10. "Tributyl Phosphate". Scorecard.
  11. Kumar, Jyothi Rajesh; Kim, Joon-Soo; Lee, Jin-Young; Yoon, Ho-Sung (18 February 2011). "A Brief Review on Solvent Extraction of Uranium from Acidic Solutions". Separation & Purification Reviews. 40 (2): 77–125. doi:10.1080/15422119.2010.549760. S2CID   95358600.