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2005 Spring

Tolyltriazole - Myth and Misconceptions:

A New Look at Tolyltriazole, its Properties, and Uses
By Peter F. Vogt, Wincom, Inc.
Introduction Due to their excellent heat transfer properties, copper and copper alloys are widely used in open and closed circuit cooling water systems. To control and reduce the copper corrosion in these systems, the water treatment industry has used benzotriazole (BTA) and tolyltriazole (TTA) along with mercaptobenzothiazole (MBT) as its main products. Due to the lower cost and performance, TTA has become the workhorse product over the years. With this, the industry has also accepted the "typical tolyltriazole odor" and its "color" as a fact, despite many complaints. It is time to take a closer look at its quality, properties and performance. In reality, tolyltriazole is a pure white compound that has no odor. Process improvements in recent years have now made it possible to provide high quality tolyltriazole without the 'typical odor" and "typical color" with improved corrosion protecting properties. The odor is caused by impurities that not only increase corrosion rates but also react with certain oxidizing biocides to form chloramines and similar compounds with an increase in the offensive odor, apparent in some cooling towers. Chemistry Chemically, tolyltriazole is a mixture of 4-methyl and 5-methyl benzotriazole. This means a methyl group replaces a hydrogen in the aromatic ring of benzotriazole. There are no chromophoric groups in the benzotriazole molecule that suggests any major color shift from the UV absorption range of the benzene ring by the addition of a methyl group. The absorption maximum for BTA and TTA with 260 and 274 nm, respectively is clearly in the UV range far away from the visual spectrum. This additional methyl group does not alter the color or odor properties of benzotriazole significantly and therefore, tolyltriazole should have the same color and odor, or in other words, the same absence of color and odor as benzotriazole, which has been accepted as white and odorless. Actually, based on the higher volatility, benzotriazole should exhibit more of an odor than tolyltriazole. The only difference is the fact that benzotriazole is made from orthophenylenediamine (OPD), a relatively pure synthesized starting material without any other isomers and significant impurities, while tolyltriazole is made from orthotoluene diamine (o-TDA), a waste stream of the polyurethane industry that contains reactive impurities such as toluidine isomers (ortho, meta and paratoluidine) and metatuoluenediamine isomers that cannot form a triazole ring with nitrite.

2005 Spring

In addition, changes in the reaction conditions can lead to other undesired side products. If the acidity in the reaction is too high, diazotation reaction leads to the formation of colored azo compounds. Incomplete reactions lead to un-reacted aromatic amino compounds or their oxidation products, and the high temperature distillation process can also lead to the degeneration of many high molecular impurities and adducts, generating new impurities if not done properly. Unlike benzotriazole, TTA cannot readily be purified by crystallization from a solvent, and rather high temperature vacuum distillation or other methods have to be used. Color and Odor It was generally believed and accepted that tolyltriazole has a burnt odor without further investigation and thoughts. These odors are very penetrating and have a high affinity to the human skin and clothing and linger on for days. In summer, when increased cooling is required and people are spending more time outdoors, complaints from nearby cooling towers are numerous. The color and the odor in tolyltriazole come from the impurities in the product that are formed from the toluidine isomers and metadiamino toluene still left in the starting material o-TDA. These impurities cannot form a triazole ring in the reaction with nitrite and rather form diazo or nitroso compounds that can condense further or react with oTDA or other intermediate products. These colored compounds, which have never been fully analyzed, are either oxidized aromatic amines or diazo compounds and polymerics that can be removed by appropriate purification methods. The diazo compounds have no known detrimental effects in the applications if they have no functional groups. However, this is not so with the aromatic amines. It is these volatile aromatic amines that not only contribute to the color but also to the odor and to increased corrosion. The vapors of these impurities penetrate plastic without direct contact of the solid and turn the plastic brown after oxidation in air, the same way as o-TDA or toluidine. By extracting the sodium salt solution of TTA (T50Na) with toluene, some of the aromatic amines have actually been isolated and analyzed. While these impurities can be removed easily by cleaning the starting material o-TDA and by purification of the crude

2005 Spring tolyltriazole, some manufacturers do not want to spend the additional time and effort to change their existing processes. If tolyltriazole is recrystallized from water or any other suitable solvent, the product can actually be isolated in the form of snow-white crystals that have no odor. This pure and clean product can be formulated to a sodium salt solution that is clear and colorless as water. Halogen Resistant Azoles To protect copper and copper alloy surfaces from corrosion, the azoles, such as benzotriazole or tolyltriazole, have to form a protective layer on the surface of the metal and capture any dissolved free copper ions. C6H4N3H + CuO C6H4N3-Cu-N3C6H4

Despite some misleading information in the trade, azoles and bleach do not react preferentially with each other; rather the azoles react with the metal surfaces and the dislodged copper ions from the corrosion by bleach. The reaction of TTA and bleach is completely reversible and at the low concentrations of bleach on the side of the free TTA and the TTA is therefore still available to protect the metal surface. C6H4N3H + HOCl C6H4N3Cl + H2O

With increased corrosion, more of the yellow metal surface is exposed and more copper ions are liberated that react with TTA to form the insoluble copper complex. Contrary to the azoles, MBT react with oxidizing biocides to form the dimmer, which precipitates and cannot react with copper anymore. In modified tolyltriazole (e.g. chlorinated tolyltriazole) the impurities that cause odor and color, have been destroyed in the reaction process of tolyltriazole with excess of concentrated bleach to form the N-chlorotolyltriazole. In a subsequent step, the N-chloro product is then rearranged to the C-chlorotolyltriazole where the chlorine rests on the aromatic ring. Therefore, the typical odor and typical colors are absent in these far more expensive products (e.g. chlorotolyltriazole). These products offer no more improvement in the corrosion protection1 but add considerable costs. Who wants to add a chlorinated aromatic tolyltriazole to his water and wastewater stream or any other chlorinated aromatic, only to reduce the odor and chlorine use? The aromatic amine impurities along with their reaction products with bleach with unknown toxic properties are also highly corrosive to yellow metal surfaces and removal automatically improves the protective properties of the product. As such, any modified

2005 Spring tolyltriazole often shows some improvements in reduced corrosion besides the absence of odor. Properties Most commercially available tolyltriazole today is either a white to pale yellow solid or in the form of a pale yellow to amber sodium salt solution. Both products have no odor or only a faint odor. Still, under price pressure, large quantities are still sold that are dark in color with a strong obnoxious odor. While the protective TTA layer can be penetrated by chloride and other corrosive species, tolyltriazole itself is very stable towards acids and alkali, and toward oxidizing biocides, (e.g. NaOCl) and it is very difficult to destroy the chemical itself. In water, tolyltriazole is stable to 200C and only with potassium permanganate is it possible to oxidize the methyl group to the carboxyl group. However, many oxidizing biocides, such as chlorites and the impurities in TTA can penetrate the protective tolyltriazole layer without destruction of the tolyltriazole, exposing more copper and copper oxide surface which then requires more TTA to bind and protect the new surfaces. In addition, the impurities in tolyltriazole readily react with many oxidizing chemicals and with hypochlorite, these aromatic amine compounds form chloramines with much stronger odor. To improve the stability of the protective layer, aliphatic side chains are required that block the approach of the corrosive ion species such as chloride and chlorite. In summary, clean tolyltriazole without odor and corrosive aromatic amine impurities is still the most cost effective "Halogen Resistant Azole". 1. Dr. Wayne Dickinson, Halogen Resistant Azoles, Buckman Laboratories, March 2003 About the Author Peter F. Vogt, Ph. D. of Wincom, Inc., (11444 Deerfield Road, Suite B, Blue Ash, Ohio 45242) can be reached by phone at 513-936-0185.