Molybdate and Non-Molybdate Options for Closed Systems — Part II ‘Susan Rey, The Nations! Colloid! Company and Gary M. Reggiani, Eastern Technologies, Inc. In part |, the authors discussed the physical attributes of @ closed system. In part ll, the authors present the various chemistries used in closed cooling water systems to control system metallurgies. They also describe the strengths and weaknesses of closed system inhibitor options and provide useful applica- tion information. Introduction ‘The first use of molybdate as a corrosion inhibitor can be traced to 1939, when two patents were issued claiming the use of molybdate for corrosion protection in alcohol-water antifreeze for automotive cooling systems."® Investiga- tion of molybdate as a corrosion inhibitor continued in the 1940s leading to the publication of the first fundamental study of corrosion inhibition by molybdate in 1951.‘ In this smdy, a mechanism of inhibition was proposed by Rob- certson. He also reported that molybdate was as efficient as nitrite and chromate for inhibiting low carbon steel cor- rosion in aerated, distilled water. Two years later in 1953, Pryor and Cohen reported that while molybdate is effec- ‘ive in aerated, distilled water itis not effective in deacrated water: Ta the next four decades, further electrochemical and surface studies were undertaken and the results published. ‘While the identification of molybdate as a corrosion inhibi~ tor, the anodic mechanism, and the window of performance ‘were of interest to corrosion specialists, molybdate was not commonly used in the 1950's and 1960's, since chromate was already in use, was very effective and inexpensive. Then in the 1970’, the carcinogenic nature of chromate became known, driving the market to shift away from chromate chemistry to other chemistries such as nitrite, molybdate, and combinations of the two. Recently, market forces have ‘once again changed as the price of molybdate has rapidly ‘escalated due to the demand for molybdate in steel produc- ‘tion in support of the growing Chinese infrastructure, ‘The high cost of molybdate has left water treaters scram- bling to seduce or eliminate molybdate as a closed system inhibitor, as a pitting inhibitor, as product tracer in open recirculating cooling gystemns,and as a product tracer in low- pressure boiler products Molybdate ‘Molybdate is classified as an anodic oxidizing inhibitor. ‘Molybdate is not effective in the absence of oxygen, but ‘works in conjunction with oxygen to form a protective oxide layer on ferrous metals.’ As ferrous fons are formed at the anode (Fe? -> Fe? + 2e'), molybdate ions react with the fer- ous ions to form-a non-protective fgrrous-molybdate com plex. This complex is then oxidized! by dissolved oxygen to form an insoluble and protective ferric molybdate complex in combination with fervic oxide.’ Furthermore, molyb- date is believed to strengthen the outermost hydrated iron oxide layer by hydrogen bonding to hydroxide groups on the surface, thus imparting a negative surface charge, which impedes aggressive chloride and sulfate ions from approach- ing the metal surface and ferrous ions from leaving the sur~ face.’ Lastly, molybdate helps to retard pit growth. When a break in the protective film occurs, absorbed molybdate is seleased and concentrates inside the pit precipitating as cither FeMoO, or as a condensed molybdate species.” Inaddition to use for fesrous metal corrosion control, molyb- date is commonly used as an aluminum corrosion inhibitor However, the mechanism for aluminum corrosion control is much less defined, but is believed to be incorporated into the protective film asa hydrated aluminum molybdate.” ‘When yellow metals are also present in the system, azoles are usually added for their corrosion protection. From a practical standpoint, the absorbance of molybdate onto the outer hydrated iron oxide layer means that when molybdate is fed to a poorly maintained system containing old corrosion products, molybdate will be consumed, leavingMolybdate and Non-Molvhdate Ontions for Closed Systems Part ll Continued the water treater wondering how it disappeared”. There a minimum dosage of 1 mg/L dissolved oxygen is require fore, prior to using a molybdate based treatment in a fouled when molybdate is used (without nitrite) to achieve opti system, the system should be cleaned to zemove existing mum zeéults corrosion products. Another implication of the molybdate ‘mechanism is that oxygen must be present, or another oxi- Use guidelines for molybdate are given in Table 1. The dos dant such as nitrite, fa molybdate treatment program is to range for molybdate is broad because the effective concen: be most effective. tration of molybdate increases substantially as chloride ions and to 2 lesser extent, sulfate ion concentration increases. “Therefore, ifa system is “tight,” ie, if there is no ingression For example, 70 mg/L molybdate (as Mo") may be effective i of dissolved oxygen from make-up watér addition or leaks, deionized or low electrolyte waters, whereas 466 mg/L melyb the molybdate program performance will be compromised . date (as Mo“) may be needed when the chloride level i and/or will require increased dosage. While the exact con- 200 mg/L." To convert from molybdate ss Mo’ to mol! centration of oxygen needed may vary based on the corro- date as MoO, multiply by 1.67. To convert from molybdat sion potential and temperature, some experts suggest that as Mo** to molybdate as Na, MoO, multiply by 2.15. Refe: ‘Table 1- Recommended Inhibitor Levels for Closed Systems Udo Cd Oe eT) Protected Saal fone: 150-100 25 NaMed,* 3 7ebS(aDhAl (177-777 as Mo, i (70-486 as Mo) ay pubtizot No) 50:50 - 60:40 Na,Mo0 NaNO, Ratio a. 6 a5105Fe FeAl 10+150- 4004400 Na Mo0,+NaNO,, 78-03(2,000 ie | Tolytiale (TA, 100% _| Ne, 506) | ATTA, 100%) reac Benzotiazole (7) 560 32,000 1,910 mg/n"/3H “Socium fetraborate pantahydrat 3200-3800 22,000 NA 000 22.000 NA NA, NA, NA 000-13,000. 320270 33.95 maT aerosol Propylene glycol 20,000.34 000 310,000 NA *6hiad AR/AMES®: 60 Acne 28/0 aeramidomeglpopynlore sd ANAMPSPAS: Aayc sc/saylanidonetiyiropybalfon cidlfonated qene Tobe Tox Classes: Hodge and Ste Seale Conny ror teed rae 1 ae or iess Worless ainsi dp (poo [Reet 0 38 vote atts 3 ose | sao 30 [wim waliiia « Sia | ssa waaeia [icovinoe aoa Is reaieaiy Tomson faemzse | mormon rte 3 [RRC [isemoormos | zworme [mow atta "Single dove wo at "Single epiation wo ain of abi; Espone fas fr de [efereae: OCOHS (Canedan Centr for Osipational Hest and Safe) esis cobs afbaneves/cheicaa50 ns (2005). 20Nitrite ‘Nitrite is an oxidizing anodic inhibitor that has been in use for many years." With the present high cost of molybdate, nitrite is often the most effective and least expensive option for controlling low carbon steel corrosion when no other factors ‘prevent its use. Nitrite functions by promoting the formation of a passive -Fe,O, film by the following reaction:'*"" 4Fe-+3NO, + 3H — 2F0,0,+NHy+ Ny Table 5 - Aquatic Tox 5 Unlike molybdate, nitrite does not EET require dissolved oxygen to function |. as a passivating inhibitor. Spticm morybeat of Closed System Treatment Compon Sn) spina maga}: 330 96 hr LG, Rainbaw tout 7,600 72h Kas tAlnaet 3100 2ahr NOEC (Minnow 17 48 hr Tun (Mosquito Fsh).75 ‘8 fr LG, Wate eal NS : 96 hr Ls Mosquta fish 530 36 hr LC, Water fea: >1.000 ma/L Assbownin Table, therecommended "| soiiun tite dosage depends on the water source, 2 but in summary the range is from a | Socium netesiiate(Ne,Si0, lov of 700 mg/L as NaNO, to a high ee - ee eee oui 36 hi Fathead minnow): 1,000 mae em, the required dose will depen r ; Se ae ontheconcrtadonofaggresiveone | Witenes Seip hemeopian (ie, chloride and sulfate ions) and the | *Se82 #P6(HPAL 50%, | 96 hr EG (Zea feb: as Solids.” system temperature. Sulfate ions inter |W fere to a greater extent with cosrosion -(ainopentamethylene- ® bonyicecidtiezine, 639%, es Cee ‘Diethjihydranyiamine (DERAY, CO. iy f i protection by nitrite than with chlo- i 48 br EC, Wapenia magnak 144 i Fide ions. A recommendation based | AUMUNIReManine DEHRS 5%." en bt unt 150 | or seers Jom beled ea on [voviO:gani filmer blends T See manufactur ow levels of aggressive ions, the mg oy 48 hr EC [api SDD gl sodium nitrite should equal the mg/L _ | Pipotessium phosphate OKFE 2" se irae ae Se raat pa chloride ion plus 250 to 500 mg/L. more than the mg/L sulfate ion.’ | Doses for chilled loops will tend to be at che low end of the range, while doses 48 br LC (Daphnia magna}. 2457 86 he LG Bluegil sons): 193.2 Gy Uy Renda tout): 23.7 (aR RFLE, apn atnagial io) Ener aera aly Sodium toiitiazole, 50% solution for hot loops will fall at the hig UL i e Simateanm a : eee : {i Bp bebo, outh 398 Pe A with temperature. As with all anodic fast Bebe ba iaigmah tea ick 4 inhibitors, under dosing nitrite can cause severe pitting. Too little nitrite ccan be worse than no nitrite. 24 hr Eby (Daphia magnal: 1.631 5 day LC (Gols 478 24 day LE (Rainbow trout 583 98 or EC Algae’ 162 PTT gel, Oaphniameghey gw as Cent suriah Tae Nitrite is not effective for controlling aluminum corrosion. If aluminum is /S0/#O@NAMPSI apseive io) °< 1a | SBR i present, an aluminum inhibitor such i | Siar LC Saino trout 4.800 v : ‘ 4Biv EC, (aphrieh:>1 529 a silica or nitrate will be needed. | ay nyypsersges aaie aE Ome Azoles are added when yellow metal hr LG Alga >1 049 and 2.120 protection i reuied, Nise i come 5 iG Daphnia imag aT IL | patible with glycol systems and com- 5 iC, fathead ‘rirnow): 61,800: 4 monly used non-cxidizing biocides. | HAMMER Srey Ce idegii 2750 ‘An inadequacy of nitrite treatment is {Ce Rainbroi bome6 000° the propensity to promote microbio- Aut (Dap magna 4980-3440 logical growth. This will be more of « | Propylene glycol Acute Fathead minnow: 4650054 200 : F Acute LC, (Sug 70,000 concern in chilled loops than in hot pte Le aon) 4,008_——Molyhdate and Non-Malyhdate Options for Closed Systems — Part | Continued loops, since bacteria and mold will not grow at temperatures exceeding 140 "R Nitifying bacteria will oxidize nitrite to nitrate, while denitrifjing bacteria will reduce nitrite to either nitrogen gas or ammonia." NOj-+5H +60 NH, + 20H In addition to the loss of protection as a result of the loss of nitrite, nitrate is also a nutrient for bacteria, whereas ammonia is aggressive to some yellow metils. Diligent ‘use of a non-oxidizing biocide regime is imperative when using a nitrite program. Some commonly’used non-oxidiz~ ing biocides are glutaraldehyde, isothiazolone and trisnitro, [tris(hydromethylnitromethane)]. Trisnitro is particularly effective at higher pH and against nitrifying and deniteify- ing bacteria. Potassium dimethyldithiocarbamate and poly- uate are also used. Often, the use of multiple non-oxidizing biocides provides best results. Conversely, oxidizing biocides | should not be used with nitrite treatments, since they will ‘oxidize nitrite ions to nitrate ions. Air ingress can also oxidize nitrite ions to nitrate ions: 2N0;+0,-+2NO, ‘Therefore, in systems having much air ingress, higher lev- els of nitrite may be needed, making biological control more difficult. Toxicity can be a concern with nitrite programs as nitrite is moze toxic than other closed system inhibitors. This | is illustrated in Table 3 with sodium nitrite having the lowest oral LD,, (rat) among closed system inhibitors and an estimated lethal dose by ingestion for humans of 1 to 2g, Furthermore, sodium nitrite has a CERCLA discharge limit of 100 Ib, Therefore, discharges of nitrite into the environment exceeding 100 Ib (dry weight) must be reported to the EPA. Humans: Sodium Nitsite: The estimated lethal dose in humans is 1 to 2g, Ethylene glycol versus propylene glycol: ‘The lethal dose of ethylene glycol in humans is 100 ml, (3-4 02)-In corn parison, propylene glycol is relatively non-toxic, Ingestion of a sizable amount of propylene glycol (over 100 mL) may cause some gastrointestinal upset and temporary central nervous system depression. The effects appear more severe in individuals with kidney problems. Molybdate/Nitrite ‘The combination of molybdate and nitrite has been shown to be synergistic and prior to the escalation of molybdate pricing, the combination was considered by many to be the treatment of choice for closéd systems. When using the combination, nitrite takes the place of oxygen in forming the protective oxide film. Molybdate forms a protective festic complex, which becomes incorporated as part of the oxide layer and/or is absorbed onto the ferrous hydroxide surface layer of the metal. The absorption imparts a negative surface charge which repels aggressive ions (ie., chloride and sulfate). Molybdate also helps to retard the growth of pits as discussed above. ‘The ratio of sodium molybdate to sodium-nitrite giving the lowest fow carbon steel corrosion rate was shown experi- mentally to be 50:50 to 60:40. Some water treaters have formulated their products accordingly with an approximate 1:1 ratio of sodium molybdate to sodium nitrite. Follow- ing this train of thought, typical use sates are 150 mg/L NaMoO, plus 150 mg/L NaNO, to 400 mg/L NaMoO, plus 400 mg/L NaNO, Other water treaters have weighted their products more towards sodium nitrite likely as a cost susp Sherer 7 Le sate nese emma)cutting consideration. Along this vein, the AWT Technical Reference & Training Manual indicates that the molybdate level can be reduced to as low as 161 mg/L Na,MoO, with 525 to 750 mg/L nitrite as NaNO, The benefits of molybdate/nitrite programs include enhanced corrosion control, a reduced propensity for pit- ‘ting over nitrite alone, and both low carbon steel and alu- minum corrosion control. (As in the case of molybdate and nitrite alone, azoles will be needéd for yellow metal corrosion control.) Disadvantages of molybdate/nitrite , programs include 2 higher cost since molybdate is still a significant component. Also, microbiological control may be difficult due to the nitrite component. Toxicity is also a concern. Molybdate/nitrite programs are compatible with commonly used non-oxidizing biocides as well as ethylene and propylene glycols. Silicates Silicates are commonly used for both ferrous and yellow metal corrosion control in soft potable water applications, ‘where minimal heat transfer is involved, In fact, the first |____Mlyhdate and Non-Molyhdate Options for Clased Systems — Part | Continued —__ proposal for using silicates for the protection of an entin water system was made by Thresh in 1922 and silicates hav been in use since then.2* Silicates are oceasi tion in high temperature systems that use deionized wate since at low hardness, calcium and magnesium silicate wil not form, and at low chloride and sulfate concentrations th protective film can form over time. nally employed for multimetal protec- Silicates are considesed to be anodic filming inhibitors ‘They have a vasiable composition of aNa,O: mSiO, Generally, a ratio of m/n of 2.5 ~3.0 is effective." With silicate treatments the protective, film develops slowly and may take weeks to-form. The film is believed to con- sist of silica gel along with ferric hydroxide precipitates Silicates provide protection for low carbon steel, yellow metals, and aluminum. Other than for potable water systems, silicates are not com- monly used as stand alone corrosion inhibitors for low carbon steel protection. However, they are often added cither for aluminum corrosion control and/or to aug- Levolor Electronic Water Level Controls “So complete you don’t need to be there.”ment the performance of other low carbon steel corrosion inhibitors. The recommended dose for scat is 50-100 mg/L, as SiO, when used alone for mulkimetal comsion control and 10-25 mg/L. as SiO, 28 adjunct for ahuminurn and copper alloys. For closed systems having both ferrous and yellow metals, the operational pH should be 8.5 to 10.5. As discussed ear~ lier, if aluminum is present, the pH should be maintained at, less than 9.0, and ideally between pHs 7.8 to 8.3 One advantage of silicates is that they do notact as a nutrient formicrobes and are therefore an option where microbiological control is difficult. A disadvantage of using silicates is the tendency for silica deposition to occur if the product is overfed, used with hard water at higher temperature or ‘where pH is not properly controlled. For example, if silica is used for aluminum corrosion control and the pH exceeds the 9.0 imit, aluminum silicate deposition may occur, which can plug nozzles and other small orifices, etc. Silicates are considered to be selatively non-toxic. The oral LD, (rat) value of 800 mg/Kg probably refeets the high pL of sodium metasilicate and overstates the toxicity of sili- cates at use levels. Business Opportunity Sf chimica vO. One Of The Leading Manufacturers ‘Of Polymer Flocculants In The World Is Pleased To Announce The Formation Of A New North American Subsidiary OSpotymer For Water Professionals Who Want To Increase Their Market Share US Polymers, Inc. Offers * Great Products at Competitive Prices + Cationic and Anionic Emulsions + Gationic and Anionic Dries + Dispersants and Defoamers + Paper Grade Chemicals. + Ground Floor Opportunity For complete details on how we can work together Contact US Polymers, Inc. at info@3fchimica.com or call 603-371-0936 www.3fchimica.com 6 Nitrate While molybdate/nitrite and nitrte/silicate are the most commonly used combinations for controlling both low casbon steel and aluminum corrosion, occasionally sodium nitrate is used in conjunction with sodium nitrite to pro- vvide the aluminum corrosion control. In fact, while nitrite isan effective low carbon steel corrosion inhibitos it ean be antagonistic to aluminum corrosion. However, the addition of nitrate overcomes this antagonism.” ‘Nitrate functions by controlling the growth of the alumi- num hydroxide film and also 2s a pitting inhibitor by the preferential reaction of nitrate with the active surfuce% ‘A study of aluminum pitting inhibition indicated that NO,> Mo0,2> Si0,?in affectverass However, 2 Stuy of aluminum la growth inhibition inieated Si0,?>.Mo0,#> NO, ineffectiveness.” ‘The secommended dose rate for controlling both aluminum and low carbon steel cosrosion is 685 to 1,371 mg/L sodium nitrate in combination with 750 to 1,500 mg/L sodium nitrite. yellow metals are present, an azole:is recommended, since neither nitrite nor nitrate provides protection egainst yellow metal corrosion. Nitrate is considered less toxic than nitrite, with its toxicity stemming from the conversion of nitrate to nitrite in the digestive tract. This conversion occurs to a greater extent in infants. Nitrite has been associated with “Blue Baby Syn- drome” or methemoglobinemia, 2 decreased oxygen-carry- ing capacity of the blood resulting in shortness of breath, bluish colored skin, other symptoms, and possibly death. HPA-Triazine Stand Alone and Combination HPA. (Hydroxyphosphonoacetic acid) was patented in 1987 for controlling ferrous metal corrosion and scaling. Electrochemical studies pesformed at the time determined that HPA operates via a cathodic control mechanism. ‘At cathodic sites on a lowr carbon steel surface, the pHL is increased due to the formation of hydroxide ions (1/2 O, +H,0 + 2e-— 20H). Calciun/EIPA salt forms and pre cipitates at the cathodic sites due to the localized high pH. Over time, the low carbon steel surface becomes covered ‘wich 2 thin calcium/HIPA film, which stifles the cathodic reaction by preventing oxygen froma reaching the metal sur face. The film is extremely thin and does not interfere with heat transfer. The suggested dosage is 50-100 mg/L. as HPA | (30-122 mg/L organic phosphate as PO,*). Ihe low a | |20% glycol, these systems become biostatic to microbes. Phosphates are a nutrient for microbes, therefore if used in water-based systems at high concentrations the control of microbiological growth would lilely be problematic, Phosphates are inexpensive and have low toxicity, unless ingested in large quantity. However, they are a nutrient for microbes and cause algae blooms in surface waters, which can cause eutrophication of ponds and lakes. oles began to be used in closed systems for controlling yellow metal corrosion. Today, tolyltriazol, (TT) and benzotsiazolé (BT) are the most commonly used azoles, however, mercaptobenzotriazole (MBT) is occasion. ally used. ‘Typical active azole doses are 10 to 50 mg/L as the sodium, salt, The azole requirement increases with increasing com centration of chloride and sulfate ions. TT and BT function by reacting with cuprous ions a cathodic sites to form a chemisorbed monolayer of cuprous azole, which acts as a barrier to the bxygen reduction reac. tion. Bridged by cuprous ions, the TT or BT molecules, form a polymeric structure across the metal surface in whieh the sing is believed to be parallel to the metal sur face.” MBT initially reacts with cuprous ions at cathod sites forming a monolayer of cuprous MBT. Unlike TT BT, the film can grow to a 1000 molecular layer thickness as follows. As cuprous ions form, they diffuse through th: Cu, layer and Cu(1)MBT film, then bridge molecules of MBT to form a three dimensional polymeric structure Skyscrapers, YoU Ce where water ee Toa * atx treatment field experience — not found in other blenders. Brochem Industies, Ine offers our own proven product line, or we will custom blerid toyour specifications. We have the fastest turnaround time in the industry, and provide * allof our customers with private label products, including customized labels, product informetion sheets and MSDSs. Ready-to-use solutions are available in'5, 15-00-55 gallon drums, totes;and bully-r- save on freight with dry dispersion chemicals, easily mixed on-site with our Formulation Station, Dry dispersion chemical are all non-hazardous, and can be shipped anywhere via UPS or Fed‘Again the slags are believed to be oriented in @ parallel fashion to the metal surface."* MBT films form most quickly, forming a film several hun dred molecules thick in 30 seconds," whereas TT or BT films takes hours to form. However, TT and BT are more tolerant to oxidation. by chlorine than MBT, and hence are more commonly used. TT has become the inhibitor of choice because TT films provide better corrosion protection during chlorination than BT films. New substituted azoles have been developed for controlling aluminum corrosion in addition to yellow metals, but these have not seen wide use in closed systems, in part due to cost, In addition to controlling yellow metal corrosion, azoles react with cuprous ions in solution and prevent them from plating out on low carbon steel or al ‘minum surfaces, which causes pitting to ‘occur. Pitting occurs because as more and more surface becomes covered with copper metal, the electron flow from the larger more inert copper cathodic area must be balanced by électron flow from the smalles, anodic area where the metal loss occurs. Azoles are moderately toxic to animals and have moderate aquatic toxicity, but usually comprise such a small percent- age of a typical closed system formulation that the toxicity level is not problematic. Dual Coupon buffering low conductivity waters and/or high temperature systems. They are often used to buffer systems treated with WCVorganic contact film former blends as well. Dispersants are usually fed at'10 mg/L to 20 mg/L to pre- ‘vent deposition of corrosion products or contaminants that could cause underdeposit attack. Typically, an AA/AMPS® ‘based copolymer is used. In the past, maleic acid/sulfonated styrene (MA/SS) copolymers were commonly used and are occasionally in use, but they are being supplanted by the more effective AAJAMPS® copolymers. aae~ ATLANTIS - febnystobiegu? your Equipment Source Heated Polypropylene Cooling Tower Control System. Idec for small, outdoor commercial cooling tower appications this tractive package provides a hected enciosure for your selection of contralier, pumps, and chemical pais. Cooling Tower Controller ‘Our web-based dual Cooling Tower Controller features 0 durable stainless stand and polypropylene board. holdess, controllers ond metering pumps available in custom Adjuncts In addition to comosion inhibitors, buf- fers and dispersants are usually added to closed system inhibitor packages. Borate is the most commonly used buffer since has a relatively high buffering capacity, and buffers out at higher pH (pH 9.3 to 9.5). Dipotassium phosphate is com- monly used 2s a buffer and anodic cor- rosion inhibitor for glycol systems as discussed earlier. Carbonates are some~ times used in nuclear power cooling sys~ tems, since borates are not permitted for use in such systems, Amines are used for ed configurations. ne eee nec aera el pee ATLANTIS TECHNOLOGIFSLLC ee SY 308 HIGH TECH Drive OAKDALE, PA 15071 7246982900 WWW.ATLANTISLLC.COM 33|BHR ! ___ Molyhdate and Non-Molyhdate Options for Closed Systems —Part || Continued —__________j Performance Monitoring , Water treatment needs to be a conservative business. The Know (to the best of your ability) the metallurgies presen, | potential. consequences of failure of these closed loops can the system's operating yolume, temperature and pressure, | ‘be costly for the ownes/operatox. For example, the cost of and the system's treatment and performance history. | || | downtime, equipment repair and replacement, and collateral i damage (ic., water leak damage, etc) can easily cost hun- Field Testing: Critical performance criteria should include | dreds of thousands of dollars! The water treatment service corrosion monitoring, fouling monitoring and chemical | company may be held liable for part or all of these expenses, residual testing (refer to Table 6, the monitoxing matrix regardless of fault, if proper monitering aid documentation shown below as a guide). Corrosion monitoring should try ty are not maintained, _ fo represent all or at least the most critical metallusgies pres st cnt in the system. Refer the Cooling Technology Institute} | | ]) Tht Key abjecives to implementing » proper monitoring standard for coupon testing to ensure proper corrosion test 1 rogram are: ing procedures is followed." A guide for rating performance based on coupon corrosion rates is listed in Table 7. | * System knowleage I | | * Flold-testing of critical performance criteria Documentation: Be sure to effectively document the eye * Documentation of observations and recommendations tem parameters, field testing results, and any observations and recommendations provide by the customer. Verb | System Knowledge: Before taking the responsibility and communication of critical observations and recommenda i accountability of treating a system, be sure to walk the system tions must be confirmed in writing. Iris also a good practict | and review the operational and design characteristics, 10 document (as explicitly as possible) the consequences of | not heeding these observations and recommendations, Table 6 - Monitoring Matrix : | ul are eas — oe pI NI Teipo Nie (SIs Hot Watar x Chilled Water x xaae| a aeaeiik K ipsa x xx K E x als | le 7 - Quant of Corrosion Rates for Closed Systems* Description eI Copper Alloys (mpy) Excel <02 10 i Good 02.005 0.1010.25 | Moderate ce “[ost008 02510035 1 Poot 081010 03510050 | Very Poor to Severe 21D 205 : “Boll BP 200), "Sanda for Conon Rete The Analyt, V2 p61. aMolybdate and Non-Molyhdate Options for Closed Conclusion ‘There is no treatment program that effectively controls cor- rosion and deposition in every application, but moze often than not, there is more than one option available for a given application. It is up to the water treater to: 1.) Obtain the ‘appropriate information on the closed system to be treated; 2.) Consider which options will work effectively, customer concerns and preferences, regulatory issues, and product pric- ing and 3.) To follow up with proper ménitosing, Informa- tion has been provided in this article to help the water treater to meet these objectives in this difficult business climate. # Special Acknowledgements ‘This document was produced by the Cooling Water Subcommittee of the AWT Technical Committee and was authored by Susan Reyand Gary Reggiani. Special thanks is given to Ben Baffardi, AL Bassett, and Jay Farmerie for their gracious contribution of time and expertise in reviewing this article. This article was pre~ sented at the 2005 AWT Annual Convention at Palm Springs, California, September 21-25, 2008. Susan Rey is the Technical Manager at Tye National Colloid Company. Ms Rey can be reached at srey@natcllcom. Gary Reggiani is the Director of Sales and Technical Marketing _for Exstern Technologies, Inc. Mr: Reggiani can be reached at ‘greggiani@acl.com Roferences: 1, Velaroich MS, Fur LPG, "aja in Cron Iiiton TR Rotan Macs Pans 25.5 0990, pp 98 2 Bags ALLS. P2347, 395,298, 8, Lampey H.US Pan 214709 193 4. Roberson WD, "Mots: and Tengen as Coren Thiet e Melina of akin Jews e be ‘Electrochemical Society, 98, 3, (1951), pp. 94-100. 5, Py Caen Me abe of Can Tiles See Madi nse foal oie Bacrokensel Gace 100 S089, pe 20-25, 6 Ldn Ea, Malis Conon Inhibit in the Pee eosin! Coston 38 pep tes ek 7. Salat M Sate Nhe Beef Messe Aiea on Fs osccoetnpey ics Be Nema Stlotone Carodon Soence 17-0972 gp M8 8. Kodama, Arbon JR, “Ee of Mo's nc die Koon fc often Sans Cong GOR Soins Sum ea 9 Ogun, Ohana Pa Ferzaton ne Serathnainiorcrhete hor 1 Repl Mecian by Malo, Cleo ‘gre Conon 0,50 oper 10 MeChue 6, Sila RL eon M18, (182) Sealy ffm Formation on Alesina a Aquos Slatons wong Ratheord EacxssngSpeatonngy’ Conodon Scena 2 pp 1009-1065, 11 Farce Dy Borin, Lange, MA MalDipine Repo Cored Sa Hemsgoe Canes, Nn Sah Glow, TRNACE 3050 5 3 stems — Part || Continued. Ee 2. Aenoss, AW, Roitaile, DB. “Conation lin by Soils Moy hassoomal of Cherry Tehasogy, ad Biotechnology, 2, (1979) pp 619-08. 1, Boffid BP, Poadaens of Cooling Water Teamenk® Calgon Corporation Buizaton Na STe<3TA, te 19608) ‘Calgon Corporation, Ptabugh, PA pa. 47-53, 14, Coben, M, Pyke R, Mais By "The Bie of ‘Tron of Cnonon by Nise Joura’ of he ‘Beenocheral Sosy, 96,4 (1949, pp 254-261, 15, Beck, A, Cohen M, Melos GA Study ofthe Eft of Chloide Tonal Formed oa on a Sodham Nive Sludens Joural ofthe Elesrochemiea Sct, 10356, (958),pp.332°38, 36 Rota BE, “Comion Con four Coating We Su” Cori, paper ao 274, (stn, Tj NACE, 1983), pp. 17. Coho, M,*A Bleguon Distraction Say of Fils ome Soan Nt Siton on ol of Phyl Chanson, 56,4 (1952) pp. 451483, 18. Conon LE, Sain IM, Nise Corson Inhibit” Mares Preton, 6,4 1867 99 55-58. 19, Heroic D, "Wate Trermeotn Chesed Syren" ‘ASRAE Jura, 45,2, 200), op. 3038 20 Robisill, DR, "Sodium Molpbaste a Cosostn Inhibit in (Coling Wier! Marerias Fetoemabe, 15,11, 0976) p5-40-44, 21, Tre]. The Anas 4, (1922), pp 459-4585, 50-505, 22, Wiggle RR, Heepadarl V,Soegkoy EA, “The Tatiana of Atoms Eig Oc thn” Meas Performan, 20,6 (983), pp. 15-28 28. Heiss H Kein N, Paes, FL. Alunieum, $4 (1978) p. 198 24 Cook, Rihana X, Tames US, Patt 469,200, 3897 25."The New Sundar Bele 575; "Belgra Marc, 1988 Eaton, Ciba Gey Pulienion No. 5322038, Ciba Geigy Wiser Catials Gown Hawome, NY 26. "All Organi Coron Inhibivos for Cloned Stems "BioLabs Power Pon] Pras [BSS], C9908) See 1-3, Sakai ee, ewrencei, OA 27.US Parent 5,292,455, 1994, 28. "Gie Your Ene Scam Bier Sym Reso Vert, with eonstp DEHA Water Textnent" QOO3, Atotina Pabtestion, Arora Chemicals Ine, Padi, PA. 29. Scbramasins, A, Nateszn,M, Maraidhace, VS. Belacishoan, K,yVaeuden, Tan Overt Vapor Phe Connon Tekiitns" Conlon, 56,2, 2000, pp M158. 30. Wiehtes A, Ski, tllmas,N,"Dicylokesaminonass itis A Vole Iokistor for Conodin Preventative Packaging Conosion, 7,9 (931) p2- 28-294 5, Sud, EG. Vernon, WH, "The Prevention of Coon Paclaging1"he Ur of Safi Seasons mr Coron lacinr i Wrappigs Joona of Apped Chenu. 2, 4 (0882) pp.166372. 52, Stig... Verzon, WH, "The Prweon of Coeon in Baskaglng IL Vaoe Phe [hiitor Journal of Aoplicd Chemin 2 4 (1952), p3 178-18. 58 Jsaby, ALCS, Pater 2580823, 1952 4. Mite BA, Karsan, MUS Puen 6085, 905, 2000 55. "Vapor Concion Inbiting Adve,” eves 498M, 198), Corte Pbleaton, Cortes Corporates, Wie Bear askway, MIN, 56 Hef, Nach NA. Tar, Si, Organic Corr Ines ‘Nesta Slstons Fre | “Iai Copper and Asin ‘Sumit Cain Carbine "Coven 83,6 (99), pp. 87-657. 7 oft BP, *Coppex Coo inthe Us Indu” Calgon Paice ‘No. 11-858, 9800) Calgon Corporation, Pitsburg BA. pp T-8. 8. saws M, Sorta, W, ‘Specuo-Elatochenicl Studies of the Carvin lnkition of Copper by Mereaptobenzthacla” Conion Sener, 9, (1979) pp 08-722 5, Pos Mi, CohesM, "The hibition ofthe Cortovon ‘fla by Same Abdi nitro Jura of oe ‘Becoochemizel Soe 005 (985) py 208-25,Pea 40, gor MJ, Cohen, M, Brown "Te Nate of ims Focmed by ‘Paevasonof roe wth Soto of Scum Phosphate” Joural of tae Eerrochemieal Soe 9,2, (1982) pp. 582° 41, Hollnder ©, May, R "The Chemistry of Azole Copper ‘Corot Inia in Cooling Waster’ pepe 0.310, (Coneion/83, Hou, TR NACE, 1968p ToL 42, "Conesion Texting Procedret—Covzsion Coupon "Teng snd Tear Bess” Hevision Date: Octobe 2000, (CTH Coe Si 14100), Cooking Tower Ine. References for Table 1 - Recommended Inhibitor Levels for Closed Systems: 1. AWTT (vacation of Wier Techoologin Reirene and Ta ‘Manus atten, Chapt 4 Coslag Weteg p83. 12 Kesles SM, “An All Organic Trestmest Approach 0 ‘Cised Lop Cooling Waser AppicatonsCosesion 88, paper ne. 218, (Houston, TX NACE, 1983) p. 1-19. S. Soft, BP, "Pandementl of Cooking Wate Tete” Cgc Pubtiation No-1l~f81A, (te 19808), Calgon Gorporason, Pasar, PA, pe 37-58, 4, HaravlcD, Fortin, G, “Advancesin Closed Syeer ebbions" Conesion/0, paper 0 659, (Houston, THe NACE, 2000), pp. 5, “Baler® 593 Coroion Initio for Clow Whee Sytems"Watecet, ‘BioLab Peblistion, (2022), SioL Water Ate Lawrenceville, GAL 6, Robiale, DR, “Sodium Molybdate « Comosion ltibitorin Cooling Wass” Mater Perfomance, 15,11, (1978), pp. 40-44 References for Tables 3 - Animal Toxicity Studies and Human Toxicity: Sedan mob Sean Molde Diynte MSDS, etoe S300), Cnn Mspecenm Solon nite: Sodus Nite MSDS, Yo 2, ‘Hae Das € 225995, Vopak USA le Sadun pettice peat Sodium Mout Pe ‘Gag on Bo Ben Dav 1-8 Tope US I Sodom st Sod Neste MSDS, Revie No ‘Bac 1005 as Seni Hyopbosphonoe act: Belo: 575 MSDS, Revision ‘No.4, Date: 12-27-1999, BioLabs, ae, “iv(aniaopenamet neato ai)-cinsine Beer $93 eerie bier Goce Was Sena) Wena, bLE Rube, BeLab Ware Addit Livecodle CX Diednhyoyaice (DEH): ancy 69% MSDS, Revo NOT team, ATOTINA Chem lee Diygeau, Pherae Dipti Phoate MSDS, nas 004 Dae 205098 Unin OSA Soom wipe Cbmtee®TT-505 MSDS Cures Die 9 TBIDRE EME Specs Grog ne 2a SDED fa). “ays: Coban TT-10 MSDS, Comet De 939-200, PMC Spas Gp nc, Dem CD50 Ra Bensoriane Cobeat29 Pate MSDS, Curent Date: 9-25-2603, PMC Splits Guap Inc, Onl LDSO (Re, Dowad LSet Bevan Benaiaole MSDS Fein De 9-16-2902, scoot ates os nbn LOSE). Sods Tetaboate Pent: Boel MSDS, Vets O60, Eanes Dre atts Gate ESRI (ols ANAMPS® Copaymer-TRC-285 MSDS, Ise Dats 10:30996 Gaon Carport [ANAMPSYS Copajen“Dipening Sssetsing wrth Goad el 10 Daa (199. BE Gooch Psbeation, BF Gone Company Spry Chand Boston Clean OF pi yen Gy Ege Glyn MSDS, Version BS ae 212 WOE Uae USA Pylce Gigs Prope Gel MSDS, tne Bre is ank Cains US ee Refine for Tale S- Aquatic Taxis Studien Sarin mye Sin Male Didate MSDS, Revision 5-21-2003, Chmax Molbéeoum. Socium state Sodium Nixie MSDS, Cust Isue Dates ‘ay 1999, General Chemial Conartin. Seam metic pete: Sd Mee Peale ‘MSDS Veto ds Eicive Dre 12-1615, Vop USA Ine Sociom niente: Sodium Nitrate MSDS, Revision No, 1, Dae: 114-2005, Baber Seni Hydiphowphonoaces acid: Bele: 575 MSDS, Revision Na 4, Date 1227-1999, Bio-Lab Toe “Ti aminopenarsaylenceutoncasd)-azine: "Bane 595. ““Canesion Iahibior for Cloned Waser Sse" 2003). Watcfiont, Biol sh Psblcaton,BioL-ab Water Addires,Lavrenceile, GA. Dieyiydegianine (DEHA: Proto 85% MSDS, Reson NLD Duk eat hoo ATOFINA Chemis Ine ‘Diparasiun Phosphate: DipausaraPhowlate MSDS, *Venion O03, Date: 9-291998, Using USA, Sodus igtnole Cobrtec®TT-S08 MSDS, Cunt ate 912-2002, PMC Species Goup, Ine [Benaosanle: Cobite®9 Flake MSDS, Curent Dat ‘e25-2003, PMC Species Gzoup In. Sodiusn Teeaborae Petabyrate: Bors sels MSDS, Version (2, Esetve Date §-2008,Unvar USA, Ic 60190 AA/AMPS® Copolymer pHeseGUARD 4500 MSDS, Tse Date 5-19-1997, Calg Corporation, Etiylone Gps Behylene Gly MSDS, Vesion ‘6, Dates8-12-2002, Unis USA, Propylene Glyct Propylene Giyeol MSDS, Bieeve ate: 1-16-2001, Unive USA, I. Chemtré!® cr100 COOLING TOWER TREATMENT 1 Conductivity Control with choice of automatic bleed Programs 4 pl Control wit choice of ac Erbase Yood 1 Temperature Monitoring, 1 Adie Food Programs (ost, role. ot). J Remote computor opsraton Cattus Today at ¥ S:yoar Electronies Warranty. estas PLUS: Easy to Use menus and sub-menvs, ¥ Over40,000 installations word since 1876, 1 Free Tochnical Support wih ores phone, fax, emalland Inteectveremote computer Leading n Automated Water Treatment Since 1976