Tetramethylammonium hydroxide
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| Names | |
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| IUPAC name
N,N,N-Trimethylmethanaminium hydroxide
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| Other names
tetramethylammonium hydroxide
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| Identifiers | |
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3D model (JSmol)
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| ChemSpider | |
| ECHA InfoCard | 100.000.803 |
PubChem CID
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| UNII |
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CompTox Dashboard (EPA)
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| Properties | |
| C4H13NO | |
| Molar mass | 91.154 g·mol−1 |
| Density | ~ 1.015 g/cm3 (20-25% aqueous solution) |
| Melting point | 67 °C (153 °F; 340 K) (pentahydrate) |
| Boiling point | decomposes |
| high | |
| Hazards | |
| GHS labelling: | |
 
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| Danger[1] | |
| H300, H311, H314[1] | |
| P260, P264, P270, P280, P301 P310, P301 P330 P331, P303 P361 P353, P304 P340, P305 P351 P338, P310, P322, P361, P363, P405, P501[1] | |
| NFPA 704 (fire diamond) | |
| Safety data sheet (SDS) | Sigma-Aldrich MSDS for TMAH·5H2O |
| Related compounds | |
Other anions
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tetramethylammonium chloride |
Other cations
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tetraethylammonium hydroxide |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tetramethylammonium hydroxide (TMAH or TMAOH) is a quaternary ammonium salt with molecular formula N(CH3)4 OH−. It is commonly encountered in form of concentrated solutions in water or methanol. TMAH in solid state and its aqueous solutions are all colorless, but may be yellowish if impure. Although TMAH has virtually no odor when pure, samples often have a strong fishy smell due to presence of trimethylamine which is a common impurity. TMAH has several diverse industrial and research applications.
Chemical properties
[edit]Structure
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TMAH is most commonly encountered as an aqueous solution, in concentrations from ~2–25%, and less frequently as solutions in methanol. These solutions are identified by CAS number 75-59-2. Several hydrates such as N(CH3)4OH·xH2O. have been crystallized.[3] These salts contain well separated Me4N cations and hydroxide anions (Me is an abbreviation of methyl group). The hydroxide groups are linked by hydrogen bonds to the water of crystallization. Anhydrous TMAH has not been isolated.
Preparation
[edit]One of the earliest preparations is that of Walker and Johnston,[4] who made it by the salt metathesis reaction of tetramethylammonium chloride and potassium hydroxide in dry methanol, in which TMAH is soluble, but potassium chloride is not:
- NMe4 Cl− KOH → NMe4 OH− KCl
Where Me stands for the methyl group, –CH3.
This report also provides details for isolation of TMAH as its pentahydrate, noting the existence of a trihydrate, and emphasizes the avidity which even the former exhibits for atmospheric moisture and carbon dioxide. These authors reported a melting point of 62–63 °C for the pentahydrate, and solubility in water measured averagely around 220 g/100 mL at 15 °C.
Reactions
[edit]TMAH is a stable compound, with a half-life longer than 61 h in 6 M NaOH at 160 °C.[5]
TMAH undergoes simple acid-base reactions to produce tetramethylammonium (TMA) salts whose anion is derived from the acid used. Illustrative is the preparation of tetramethylammonium fluoride:[6]
- NMe4 OH− HF → NMe4 F− H2O
- Solutions of TMAH may be used to make other tetramethylammonium salts in metathesis reactions with ammonium (NH4 ) salts. For example, tetramethylammonium thiocyanate may be prepared from ammonium thiocyanate as follows:[7]
- NMe4 OH− NH4 SCN− → NMe4 SCN− NH3 H2O
TMAH and many other TMA salts containing simple anions thermally decompose into trimethylamine.[8] Dimethyl ether is a major decomposition product rather than methanol.[9] The idealized equation is:
- 2 NMe4 OH− → 2 NMe3 MeOMe H2O
Properties
[edit]TMAH is a very strong base.[10]
Uses
[edit]One of the industrial uses of TMAH is for the anisotropic etching of silicon.[11] It is used as a basic solvent in the development of acidic photoresists in the photolithography process, and is highly effective in stripping photoresists. TMAH has some phase transfer catalyst properties. It is also used as a surfactant in the synthesis of ferrofluids and to inhibit nanoparticle aggregation.
TMAH is one of the most common reagents used in thermochemolysis, an analytical technique involving both pyrolysis and chemical derivatization of analytes.[12]
Wet anisotropic etching
[edit]TMAH belongs to the family of quaternary ammonium hydroxide (QAH) solutions and is commonly used to anisotropically etch silicon. TMAH is preferred over sodium or potassium hydroxide in applications that are sensitive to metal ion contamination.[13] Typical etching temperatures are between 70 and 90 °C and typical concentrations are 5–25 wt.% TMAH in water. In case of (100) silicon etching rates generally increase with temperature and decrease with TMAH concentration. Etched (100) silicon surface roughness decreases with increasing TMAH concentration, and smooth surfaces can be obtained with 20% TMAH solutions. Etch rates are typically in the 0.1–1 micrometer per minute range.
Common masking materials for long etches in TMAH include silicon dioxide (LPCVD and thermal) and silicon nitride. Silicon nitride has a negligible etch rate in TMAH. The etch rate for silicon dioxide in TMAH varies with the quality of the film, but is generally on the order of 0.1 nm/minute.[11]
Toxicology
[edit]The tetramethylammonium ion [14] affects nerves and muscles, causing difficulties in breathing, muscular paralysis and possibly death.[15][16] It is structurally related to acetylcholine, an important neurotransmitter at both the neuromuscular junction and autonomic ganglia. When it acts as an agonist, this structural similarity is reflected in its mechanism of toxicity – it binds to and activates the nicotinic acetylcholine receptors, although they may become desensitized in continued presence of the agonist. The action of tetramethylammonium is most pronounced in autonomic ganglia, and so tetramethylammonium is traditionally classified as a ganglion-stimulant drug.[17]
The ganglionic effects may have contributed to deaths following accidental industrial exposure. "Chemical burns" induced by this strong base are also severe. There is evidence that poisoning and even death can occur through skin-contact with low concentration solutions of TMAH.[16][18]
See also
[edit]References
[edit]- ^ a b c d Sigma-Aldrich Co., Tetramethylammonium hydroxide pentahydrate. Retrieved on 2015-04-06.
- ^ Mootz, Dietrich; Seidel, Reinhard (1990). "Polyhedral clathrate hydrates of a strong base: Phase relations and crystal structures in the system tetramethylammonium hydroxide-water". Journal of Inclusion Phenomena and Molecular Recognition in Chemistry. 8 (1–2): 139–157. doi:10.1007/BF01131293. S2CID 95063058.
- ^ Hesse, W.; Jansen, M. (1991). "Polymorphie von Tetramethylammoniumhydroxid-Pentahydrat, NMe4OH.5H2O, und Kristallstrukturen der Raumtemperatur- und Tieftemperaturform". Zeitschrift für Anorganische und Allgemeine Chemie. 595: 115–130. doi:10.1002/zaac.19915950112.
- ^ Walker, J.; Johnston, J. (1905). "Tetramethylammonium hydroxide". J. Chem. Soc., Trans. 87: 955–961. doi:10.1039/ct9058700955.
- ^ Marino, M. G.; Kreuer, K. D. (2015). "Alkaline Stability of Quaternary Ammonium Cations for Alkaline Fuel Cell Membranes and Ionic Liquids". ChemSusChem. 8 (3): 513–523. Bibcode:2015ChSCh...8..513M. doi:10.1002/cssc.201403022. PMID 25431246.
- ^ Christe, K. O.; Wilson, W. W.; Wilson, R. D.; Bau, R.; Feng, J. A. (1990). "Syntheses, properties, and structures of anhydrous tetramethylammonium fluoride and its 1:1 adduct with trans-3-amino-2-butenenitrile". Journal of the American Chemical Society. 112 (21): 7619–7625. doi:10.1021/ja00177a025.
- ^ Markowitz, M. M. (1957). "A Convenient Method for Peparation of Quaternary Ammonium Salts". J. Org. Chem. 22: 983–984. doi:10.1021/jo01359a605.
- ^ Lawson, A. T.; Collie, N. (1888). "The action of heat on the salts of tetramethylammonium". J. Chem. Soc., Trans. 53: 1888. doi:10.1039/CT8885300624.
- ^ Musker, W. Kenneth. (1964). "A Reinvestigation of the Pyrolysis of Tetramethylammonium Hydroxide". Journal of the American Chemical Society. 86 (5): 960–961. doi:10.1021/ja01059a070.
- ^ Stewart, R.; O'Donnell, J. P. (1964). "Strongly basic systems: III.The H_ function for various solvent systems". Can. J. Chem. 42 (7): 1681–1693. doi:10.1139/v64-251.
- ^ a b Thong, J. T. L.; Choi, W. K.; Chong, C. W. (1997). "TMAH etching of silicon and the interaction of etching parameters". Sensors and Actuators A: Physical. 63 (3): 243–249. Bibcode:1997SeAcA..63..243T. doi:10.1016/S0924-4247(97)80511-0.
- ^ Shadkami, F.; Helleur, R. (2010). "Recent applications in analytical thermochemolysis". J. Anal. Appl. Pyrol. 89: 2–16. doi:10.1016/j.jaap.2010.05.007.
- ^ Liang, Wensheng; Kho, Teng; Tong, Jingnan; Narangari, Parvathala; Armand, Stephane; Ernst, Marco; Walter, Daniel; Surve, Sachin; Stocks, Matthew; Blakers, Andrew; Fong, Kean Chern (2021-04-01). "Highly reproducible c-Si texturing by metal-free TMAH etchant and monoTEX agent". Solar Energy Materials and Solar Cells. 222: 110909. Bibcode:2021SEMSC.22210909L. doi:10.1016/j.solmat.2020.110909. ISSN 0927-0248. S2CID 230573829.
- ^ Note that studies of the pharmacology and toxicology of TMA have typically been carried out using TMA halide salts - the hydroxide ion in TMAH is too destructive towards biological tissue.
- ^ Anthoni, U.; Bohlin, L.; Larsen, C.; Nielsen, P.; Nielsen, N. H.; Christophersen, C. (1989). "Tetramine: Occurrence in marine organisms and pharmacology". Toxicon. 27 (7): 707–716. Bibcode:1989Txcn...27..707A. doi:10.1016/0041-0101(89)90037-8. PMID 2675390.
- ^ a b Yang, Y.; Kim, S.M.; Park, J.S. (2022). "A case of cardiac arrest after dermal exposure to 2.38% tetramethylammonium hydroxide" (PDF). J. Korean Soc. Emerg. Med. 33 (3): 322–325.
- ^ Bowman, W.C. and Rand, M.J. (1980), "Peripheral Autonomic Cholinergic Mechanisms", in Textbook of Pharmacology 2nd Ed., Blackwell Scientific, Oxford 10.21
- ^ Lin, C.C.; et al. (2010). "Tetramethylammonium hydroxide poisoning". Clin. Toxicol. 48 (3): 213–217. doi:10.3109/15563651003627777. PMID 20230335. S2CID 3393943.