AQUEOUS CORROSTON AND DEPOSITTON 18 METAL SYSTRIS Corrosion of {ron, steel and other active metals, such as zine, in aqueous media {is basically an electrolytic process which involves anodic and cathodic areas (corrosion cells) on the metal surface. ‘Innunerable microcells are generally present because of differences in metal stress (e.g. {rom cutting or other cold vork), surface deposits, Like a{ll scale and corrosion deposits, setallographic inclusions, and other son uniformities, Larger corrosion cells can result from difference in teuperature, flow rate, oF concentration of dissolved substances, as vell as fron Joining dissintiar mecals in vhat are called galvanie couples. The anode and cathode of a corrosion cell may be close coupled, as in a steel pipe attached to a bronze pump, or far renoved from one another and connected by long-line current flow. An aerated section of pipe (eathode) Feacting with another in airefree vater (anode) {# an exanple of the lacter. Whatever the source and size of the corrosion cell, the basic corrosion process As essentially that shown in Figure 1, Yetal dissolves at the anode to form electrically charged atons (ions) and release electrons vhich pass through the meta to the cathode land react with hydrogen fon (I) in the ater to form atonie hydrogen (1°). Tats deposits on the cathode and tends to protect (polarize) it. che initial driving force for the process (electrical potential) depencs upon such factors as the relative sizes of the anode and cathode, the distance and electrical resistance separating them, the corrodability (activity) of the metal involved and the cosposition of t water. The extent to which corrosion proceeds depends upon a variety o! equilibrium reactions and depolarization processes, as well as upon certain physical Factors. 1.1 PERTINENT ELECTRODE REACTIONS Because water foaizes to form both # and (O:)~ ons, deposition of atomic Inydrogen on the cathode area leaves ar excess of (OH) ions in surrounding water. In the case of corroding iron, these react with Fe ions as the tuo migrate Yovard the areas of opposite electrical charge and form ferrous hydroxide, Fe(Ok) 2, a relatively insoluble product. If dissolved oxygen i¢ present, this conpound is converted to Fe(O!!) which collects upon and tends to provide sone protection to the metal surface. A-sinilar reaction occurs If the vater contains caletun (Ca**) and bicarbonate (HCO}") ions which is normally the case in natural waters. Hydroxy1 fon (Oi) combines with Cat* to forn calcium hydroxide, Ca(Ci)3, vitch in turn reacts with HCO;~ to Form relatively insoluble caleiun carbonate, CaC03. Depending upon other vater quality factors, this deposit, like Fe(Olt)3, may deposit and tend to prevent (niibie) the corrosion reaction by polarizing the anode as well as the cathode and thereby reducing the electrical potential (corrosive driving force) between then. Orher important electrode reactions have the opposite effect and cond to promote corrosion. Sodium ion, Hat, reacts with excess (Oli)~ to produce highly Soluble NaOH which increases the pli of the cathodic area, as vell as its corrosion potential relative to the anode. The negative fons, Cl, SO,-~ and NOs", which migrate to the anode have no corrosion inhibiting properties and actually tend to penetrate protective films and, thus, Increase corrosion rates. If dissolved oxygen is present, Fett nay react with Ci” to form ferric chloride, FeCly, hich hydrolyzes to produce hydrochloric acid, HCL, and markedly IncreasecaTHODE +h ANODE 4 CATHODE —+} Fig. 1 FR(M, (DEPOSIT CORRODED AREA caret Sree + Fe(OH), DEPOSIT “~ Electrolytic Corrosion Process (CASINGWater ondived 4 tool Felon 0.80] 060 0.40 0.20 Eh. IN VOLTS 0.90 0.20| 0.40 0.60 0.80 Figure 14. Fields of stability for solid and dissolved forms of iron as a function of Eh and pH at 25°C and 1 atmosphere pressure. Activity of sulfur species 96 mg/L as SO” ,carbon dioxide species 61 mg/L as HCO, . and dissolved iron 56 pg/t.