Corrosion Inhibition With Sodium Nitrite Author(s): Jess Beecher, Charles Dinkel and Steve Corwin Source: Journal

(American Water Works Association), Vol. 51, No. 9 (SEPTEMBER 1959), pp. 1175-1180 Published by: American Water Works Association Stable URL: http://www.jstor.org/stable/41256143 . Accessed: 02/03/2014 06:27
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Corrosion InhibitionWith Sodium Nitrite

Jess Beecher, Charles Dinkel, and Steve Corwin
Director A contribution to theJournal of Tech.ServbyJessBeecher, ices; CharlesDinkel,StaffEngr.; and Steve Corwin,StaffEngr., all of E. F. Drew & Co., New York. nitritehas been used for Nature of Tests corrosionof manyyears to inhibit and Experienceswithsodiumnitrite metalsby water. In functioning as an a combination zinc of sodium nitrite, anodic inhibitor, sodium nitriteoxi- sulfate, and polyphosphate as corrosion dizes ferrous ions to ferric ions at iron inhibitors for an open, circulating and steel surfacesto produce a very cooling-water systemare discussed in thin adherentfilmof ferricoxide on the paragraphs that follow. The reanodic areas (1, 2). Use of an in- sults of tests made for evaluation of sufficient concentration of the inhibitor these inhibitorsare reported. The or use of a waterhavingtoo low a pH tests were the determine to designed can cause corrosion to occur only degree of protectionprovided by the locally (1). If presentin a sufficientinhibitors. sodium nitriteis an efconcentration, The data were obtainedfrom a study ficientcorrosioninhibitor;if present of test corrosion specimensexcoupon in an insufficient it inconcentration, posed in the cooling-water system hibitsonly the most dangerouscorro- when was used as only sodium nitrite sion (3). an inhibitor and when a combination The use of zinc salts in small con- of sodium nitrite,zinc sulfate, and centrationsin water for preventing polyphosphate was used. corrosionof metals was discussed by The authors realize that the corroThornhillin 1945 (4). Evans (3) sion data obtained from the exposed zinc sulfateas a cathodic corrosion test specimens are not neceshas classified corrosion inhibitor.Wyllieand Chees- sarilya truemeasureof the rateof cormetalpartsof that the additionof rosionof the component man (5) reported must 0.05 per cent sodium hexametaphos- the systemand that limitations be imposedon the interto consequently phateand 5 per cent sodiumnitrite sea water gave a high degree of pro- pretationof the corrosion test data. tectionagainst the corrosionof steel The corrosiondata obtainedfromthe and that the additionof 0.01-0.02 per exposed corrosiontest specimensmay be consideredindications to nevertheless cent of sodium hexametaphosphate mixtures of 3 per cent sodium nitrite of the type and severityof corrosion and 1-2 per cent zinc acetatehavinga in the equipment. pH of 6.2-6.7 gave completeprotec- The cooling tower used in these extookplace. perimentsis a natural-draft tower in tion,but slightprecipitation
1175

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1176

BEECHER, DINKEL, CORWIN

Jour. AW WA

which water is used in air compres- by evaporation, windage,leakage, and is 7.6 gpm. rate bleedoff sors and coolers. The circulation for cooling water is 450 gpm. The of cooling water leaving Cooling System temperature The cooling systemconsistsof carthe towerbasin is 50F in winterand brass valves,and coolrewater bon steelpiping, in 90F summer; cooling ers has tower the to having copper tubes and carbon temperatures turning of 62 and 102F in winterand sum- steel tube sheets. Prior to 1956, freof piping mer, respectively. Evaporation loss, quentand costlyreplacements and extensivemaintenance of the and fittings based on the rate of circulation
TABLE 1 Waters and Untreated and Treated Cooling ofMakeup TypicalAnalyses
Water Type Cooling, Untreated (pH 6.7) Cooling, With NaNOa (pH 7.5) Cooling,With NaNO?, ZnSO4, and Polyphosphate (pH 6.5)

item

TiA^^r, MakeuP (pH 6.6)

- ppm Concentration

as CaCO3 Total alkalinity as CaCOs Total hardness as CaCO3 Ca Hardness as CaCO8 Mg hardness as Cl Chloride SulfateasSO4 Silica as SiO2 Dissolvedsolids No inhibitors Withinhibitors and sodium Total sodiumnitrite as NaO2 nitrate as NaO2 Sodiumnitrite as PO4 Total phosphate as PO4 Poly phosphate Zincas Zn

29 47 26 21 7 30 8 107

36 180 117 63 28 165 27 351

45 137 90 47 23 173 21 375 1,355 980 950

31 150 92 58 25 190 26 377 810 400 295 25 ^ **

cooling water, is 1.2 per cent, and were requiredbecause of severe genCorrowindage,or driftloss, is 0.5 per cent. eral and localized corrosion. to sion relatively transported products, Bleedoff takes place intermittently some formed locations, once a week. Windage or driftloss slow circulating Ob j ectionable troublesome deposits. of limits the cycles of concentration growthsof algae were presentin the makeupwaterto as fewas 3,whereas coolingtower. as manyas tencyclescould be allowed. The water capacityof the systemis Treatmentof Cooling Water Sodium pentachlorophenate was 22,000 gal. The amount of makeup waterrequiredto replacelosses caused slug fed as a regular treatmentto

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Sep. 1959

CORROSION INHIBITION

1177

40 ppm in the coolingwater introduce at the time of feeding,and a quaternary ammoniumcompoundwas perito odically slug fed as a supplement 6 ppm in the cooling water introduce to rid the system at the timeof feeding of algae and prevent any future growths. From October 1956 to September1957, a solutionof sodium nitritewas gravityfed to the systemin amount to maintain the a sufficient concentrationof sodium nitrite as 1,000ppm. NaNO2 at approximately From October 1957 to May 1958, and a comsolutionsof sodiumnitrite binationof zinc sulfateand polyphos-

nating the drinkingwater with the cooling water. Typical analyses of makeup water, untreated cooling water,coolingwater treatedwith sodium nitrite, and cooling water treated with a combination of sodium nitrite,zinc sulfate, and polyphosphate are outlined in Table 1. Corrosion Tests Corrosion tests were run with 4 X 1 X i^-in. low carbon steel coupons which were cleaned and preweighed. Prior to initial weighing, surface dust was removed from the

TABLE 2 TestData, January-April 1957 Corrosion

r^.,^., Coupon No. t~ *n* Installation Date c,~,,i Removal Date Exposure Ti days Initial Weight g Final Weight g Weight Loss g Corrosion Rate X 1,000 in./yr

121 119 126

Jan.5 Jan.5 Jan.5

Feb. 9 Mar. 5 Apr. 5

35 60 90

30.1331 30.1523 30.0402

29.7569 29.5673 28.7875

0.3762 0.5850 1.2527

5.15 5.6 5.3

phate were gravityfed to the system in sufficient amounts to maintainthe concentrationof sodium nitrite as 300 ppm and NaNO2 at approximately the concentrations of zinc as Zn++ and as PO4~~~ at approxipolyphosphate mately20 ppm. More of each of the inhibitors to mainwas requiredat first tain the desired concentrations;the amountneeded leveled off with time. Because the blowdown (bleedoff) water from the cooling system cona check was tained toxic constituents, made to make sure that the waste intoa waste diswaterwas discharged It was also line. necessaryto posal thattherewere no cross conascertain nections between the cooling system watersupplyin order and thedrinking of contamito preventany possibility

specimensand theywere degreasedin acetone and ethyl ether. Series of corrosiontests were run withsodiumnitrite and as an inhibitor with a combination of sodium nitrite, zinc sulfate, and polyphosphate as an inhibitor. Specimens were suspended in the basin of the cooling tower close to the suction line to the circulating pump. This site was chosen because it was felt that the water moved more rapidlythere than at any other location in the tower basin. Coupons were removedin pairs at successive intervalsduringthe test periods for study and evaluation. After exposure the specimens were : processedand evaluated as follows 1. Examination was made with a hand lens.

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1178

BEECHER, DINKEL,CORWIN

Jour. AW WA

2. The specimens were photographed. 3. The specimenswere cleaned with dilute inhibitedacetic acid according to the procedureoutlined in ASTM D935-49 (d), thendried and weighed. 4. Visual and microscopic examinationswere made. 5. Corrosion data were calculated.

Water Analyses The averagepH valueof untreated was6.7,andtheapproxiwater cooling mate Langeliersaturation pH value was 8.5 at 50F, 7.9 at 100F, and 7.4 at 150F. The cooling water as had a corrosive therefore tendency itpassedthrough andequipthepiping

Fig. 1. Appearanceof Test CouponsAfter Various Exposure Conditions

The coupons in theupper shown to sodium wereexposed nitrite alonefor photographs 60 days {leftpair) and 90 days (rightpair); thosein thelowerphotographs were zinc sulfate, and poly exposedto nitrite, phosphate for 60 days (left pair) and 90 days (rightpair).

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Sep. 1959

CORROSION INHIBITION

1179

mentof the system. This tendency higher 7 anda combination than ofzinc airborne sulfate and was frequently increased by polyphosphate performs from boilerstackgases bestat pH valuesof less than7, it is acidicmatter thatwhenthepH the cooling tower. The pH theauthors' opinion entering valuedropped to a lowof6.2 and fluc- value of cooling water fluctuates in therange6.2-7.8. This ac- through a relatively wide range,for tuated alka- example,6.0-8.0, a propercombinacounts fortheless thanexpected sulfate tionof all the above inhibitors would and morethanexpected linity in thecooling water. BecausethepH be idealforcorrosion control. value averagedapproximately 7.0, a decision was madenotto practice pH Resultsof Tests control. Table 2 showsdata obtained during thata certain a 90-daytestperiodwhensodium The analyses indicate nito ni- triteonly was used as a corrosion of nitrite amount of conversion thescope inhibitor. trate occurred.It is beyond themechanism ofthis article to explain reaction. Wyllie a301 I I 1 I I I I I I I I I of the conversion thatthe x 025 and Cheesman (5) reported in solutions 0.20 ^concentration of nitrite " used as inhibitors does not showany ^7 0.15 that and measurable onlyslight 5 o.io change ratiocan I 0.05 in thenitrite-nitrate changes be detected. They further reported, I Ql 1 I 1 I I 1 I 1 I 1 I Mar. Feb. Apr. however,that under some circum- S 1958 nitrites stances changes may undergo and Fig. 2. Effect of TreatmentWith.Zinc, in thepresence of tfon hydroxide and Nitrite Polyphosphate, even or yield ammonia,nitrogen, nitrates. used were: The quantities of inhibitors were not in- zinc as Zn, 20 ppm; polyphosphate The test specimens as of the PO*, 20 ppm; nitriteas NaN02, 300 stalleduntilthe concentration had beenadjusted. Of par- ppm. As can be seen, the additionof inhibitors reduced the corrosion ticularinterest was that beforethe these inhibitors constant level. the cooling rateand heldit at a nearly of the inhibitors addition and a waterhad a turbid appearance that nitrite sodium the addition The dataindicate after color; shortly dirty to a de- alone held the rate of corrosion the turbidity of the inhibitors, than5 creased and the color almost dis- valueofnearor slightly higher appeared. An analysisof the sus- expressedas inchesper year times of the cleaned showedit to be pre- 1,000. Examination pendedmatter showedthat the corrosion ironoxides. specimens dominantly as localizedcorrosion.FigSlightly higherdosages of the in- occurred of specimens to main- ure 1 showsphotographs wereneededinitially hibitors 60 and 90 days'exposure. This after concentrations. tainthe desired is characteristic of the typeof corro- It was the authors'opinionthatif to stepscould be takento halt localized sioninhibitors used,and is thought film formation. be due to initial corrosion, very goodprotection against would be obtained. One best corrosion nitrite Becausesodium performs was to increase considered at pH values procedure inhibitor as a corrosion

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1180

BEECHER, DINKEL, CORWIN

Jour. AW WA

corrosion an- low,a highrateof localized theconcentration of theinhibitor; can occur. theconcentration other was to decrease and polyphosphate oftheinhibitor anduse complementary Zinc sulfate perwith sodiumnithat formsynergistically with the expectation inhibitors, inhibitors to halt the actionof the inhibitors wouldbe triteas corrosion from acalmost latter The course of corrosion right completely synergistic. tionwas taken. the start. The actionof zinc sulfate the soin helping that and polyphosphate The curvein Fig. 2 indicates theuse ofreduced nitrite whena combination of sodium nitrite, dium permits nitrite. of sodium zinc sulfate, and polyphosphate was concentrations used as an inhibitor, corrosion was rate. Acknowledgments haltedand held to a negligible thanks wishto extend After in thesystem, The authors 90 days'exposure had the same appear- to A. N. Wilson (chiefdistrict the specimens engiance as they had beforeexposure. neer), C. F. Verrone(district engiof which The pointdata from the curve neer),and R. C. Putnam(director all of thePowerChemicals are shown was established in Table 3. research),
TABLE 3 1958 Corrosion TestData, January-March

c^r aie. ^g, -c- mi a,

205 206 207 208 Jan.15 Jan.15 Jan.15 Jan.15 Jan. 29 Feb. 12 Mar.15 Apr.15 14 28 59 90 24.9195 23.8985 24.0500 23.3028 24.9103 23.8883 24.0164 23.2700

"ff1 ,,HL
0.0092 0.0112 0.0336 0.0328 0.22 0.16 0.19 0.13

their The relationship ofE. F. Drew& Co.,for used in calculatingDivision data. in assistance collecting the rateof corrosion is:
c_

2 X daysexposure '

/jX365

('w*'

References wi/
1. Wachter, A. SodiumNitriteas Corrosion Inhibitorfor Water. Ind. Eng. 37:749 (1945). Chent., of CorroInhibition 2. Hoar, T. P. Nitrite sion: Some Practical Cases. Corrosion, 14 63 (1958). Pas3. Evans, U. R. Metallic CorrosionGreen andProtection. Longmans, sivity & Co. (2nd ed.. 1948). and 4. Thornhill, R. S. Zinc,Manganese, ChromicSalts as CorrosionInhibitors. 37:706 (1945). Ind. Eng. Chem., 5. Wyllie, D. & Cheesman, G. C. N. Sodium Nitriteas an InhibitorAgainst the Attack of Sea Water on Steel. /. Soc. Chem.Ind.,68:165, 209 (1949). 6. ASTM StandardMethod of Corrosivity Test of Indirtrial Water (NDHA Method)- ASTM D935. Am. Soc. Pa. (1949). Materials,Philadelphia,

in whichC is the corrosion rate (in inches per year); ,is the penetrated of the coupon (in initialthickness ofthe is initial the ; w1 inches) weight is the final and ; w2 (in grams) coupon the of coupon(in grams). weight Conclusions ofsteelspecimens Corrosion bycoolthe inhibited be water can through ing a nitrite.If, however, use of sodium of sodiumniconcentration sufficient or if the pH triteis not maintained, too water becomes valueofthecooling

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