Corrosion indices Langelier

When the number of concentrations of the circulating water is in the order of 3-7, some of the salts dissolved can exceed their solubility limits and precipitate, causing scale formation in pipes and coolers. The purpose of the treatment of the cooling water is to avoid scale formation. This is achieved by the injection of sulfuric acid to convert Ca and Mg carbonates (carbonate hardness) into more soluble sulfates. The amount of acid used must be limited to maintain some residual alkalinity in the system. If the system pH is reduced to far below 7.0, it would result in an accelerated corrosion within the system. As stated earlier, scale formation and/or corrosion tendency is defined by the Saturation Index (Langelier Index) and Stability Index (Ryznar equation). 

Langelier Saturation Index—Ideally, maintain between -0.5 and +0.5 A negative LSI indicates corrosion tendencies. A positive LSI indicates CaCOs scaling tendencies. 

LSI (Langelier Saturation Index) an indication of the corrosive (negative) or scale-forming (positive) tendencies of the water. Hardness the total dissolved calcium and magnesium salts in water. Compounds of these two elements are responsible for most scale deposits. Units are mg/l as CaCOs. 

Although the Langelier index is probably the most frequently quoted measure of a water s corrosivity, it is at best a not very reliable guide. All that the index can do, and all that its author claimed for it is to provide an indication of a water s thermodynamic tendency to precipitate calcium carbonate. It cannot indicate if sufficient material will be deposited to completely cover all exposed metal surfaces consequently a very soft water can have a strongly positive index but still be corrosive. Similarly the index cannot take into account if the precipitate will be in the appropriate physical form, i.e. a semi-amorphous egg-shell like deposit that spreads uniformly over all the exposed surfaces rather than forming isolated crystals at a limited number of nucleation sites. The egg-shell type of deposit has been shown to be associated with the presence of organic material which affects the growth mechanism of the calcium carbonate crystals . Where a substantial and stable deposit is produced on a metal surface, this is an effective anticorrosion barrier and forms the basis of a chemical treatment to protect water pipes . However, the conditions required for such a process are not likely to arise with any natural waters. 

The effect of pH on the corrosion of zinc has already been mentioned (p. 4.170). In the range of pH values from 5 -5 to 12, zinc is quite stable, and since most natural waters come within this range little difficulty is encountered in respect of pH. The pH does, however, affect the scale-forming properties of hard water (see Section 2.3 for a discussion of the Langelier index). If the pH is below the value at which the water is in equilibrium with calcium carbonate, the calcium carbonate will tend to dissolve rather than form a scale. The same effect is produced in the presence of considerable amounts of carbon dioxide, which also favours the dissolution of calcium carbonate. In addition, it is important to note that small amounts of metallic impurities (particularly copper) in the water can cause quite severe corrosion, and as little as 0-05 p.p.m. of copper in a domestic water system can be a source of considerable trouble with galvanised tanks and pipes. 

Domestic heating coil internal corrosion. Where naturally soft or lean city water is supplied and the Langelier Saturation Index (LSI) is below -1.0, acid corrosion takes place as a result of the acidic nature of the water. This water often has a high dissolved gas content, which additionally leads to pinhole corrosion. Where water velocities are too high (say, over 6 ft/s 1.8 m/s) the protective oxide layer is stripped off and erosion corrosion takes place. 

The Langelier Saturation Index (LSI) is a method for quantifying the scaling or corrosion tendency of water. It was originally applied to cooling water. The LSI is based on the pH and temperature of the water in question as well as the concentrations of TDS, calcium hardness, and alkalinity. 

If the actual pH is below pH, the result is a negative index and CaCO will dissolve in the water. It is also generally assumed that this will indicate the water to be corrosive towards steel in the presence of oxygen. On the other hand if the Langelier index is positive (i.e. pH > pH,) and the water is saturated with CaCO scale formation is likely to occur. 

The Langelier index (see Chapter 14) suggests that the water is near equilibrium but it could have a slight tendency to either scale formation or to corrosion depending on local conditions. 

LANGELIER SATURATION INDEX - An index (SI) based upon the pH of saturation of calcium carbonate used to determine the tendencies of a water supply toward corrosion or scaling. A positive index indicates scaling tendencies a negative one means corrosion tendencies. (Langlier Index = pH - pHs, where pH = actual pH of water and pHs = pH at which water having the same alkalinity and calcium content is just saturated with calcium carbonate. 

For calculating pHj in order to solve the equation, there are tables for values of pK - pK ) at various dissolved solids contents and various temperatures. The calcium content and alkalinity can be easily determined by the plant chemist. If the Langelier index (pH-pH,) is zero, the water is just saturated with CaCOj. If the index is positive, the water is supersaturated with and will tend to deposit CaC03 as well as be more or less scale forming and noncorrosive. If the index is negative, the water tends to be corrosive. 

The primary factor affecting long-term corrosion is whether a water does or does not form scales, which in turn depends on hardness and pH. This property is determined by calculating the Langelier index or the Ryzner stability index. The simpler form of Langelier s equation is ... 

The solubility of elements in freshwater is limited and the solubility of calcium and magnesium carbonates are of particular importance in freshwaters. The solubility of carbonates is inversely proportional to the temperature of the water. In other words, as the water temperature increases, calcium and magnesium carbonates become less soluble. If the solubility decreases sufficiently, carbonates will precipitate and form a scale on the surfaces of the system. This scale can provide a protective barrier to prevent corrosion of the metallic elements in a system. Excessive scale deposits can interfere with water flow and heat transfer. The quality of the scale is dependent on the quantity of calcium that can precipitate as well as water flow and the chloride and sulfate content of the water. The tendency of water to precipitate a carbonate scale is estimated from corrosion indices such as the Langelier Saturation Index (LSI) and Caldwell-Lawrence calculations [6-8] which use calcium, alkalinity, total dissolved solids, temperature and pH properties of the water. Other indices, such as the Ryznar Index... 

Equilibrium curves can be determined and, on the basis of a given water composition, used to establish whether a water is scaling (not corrosive) or non-scaling (corrosive). Many different methods have been proposed for prediction of the formation of CaCOa. Commonly used equations or indices are the Langelier Saturation Index, LSI (Langelier, 1936) and the Stability Index, RSI, a modification of the LSI proposed by Ryznar (1944). In the German literature the LSI is known simply as the Saturation Index, Is (Morbe et al., 1987). These indices describe the algebraic difference between the actual pH of the water and the calculated pH at which it would be saturated with calcium carbonate ... 

Several attempts have been made to develop an index that would predict whether a water is corrosive or not, however, these attempts have not been successful. Several indices have been developed over the years. Some of these indices can be used in corrosion control programs. The two most common indices used are Langelier Saturation Index (LSI) and Aggressive Index (AI), which are summarized below. 

The solubility product of salt changes with temperature and the concentration of the ions present in solution. In oilfield brines, if the surface solubility produced is smaller than their solubility product under down-hole formation, scale formation would occur. Under such conditions, the water is called unstable water. The StabiUty Index (S/) is used to predict the tendency of ions to form scales from oilfield brines which are highly corrosive and encountered during drilling process. The Stiff-Davis Modification of the Langelier equation is used to predict calcium carbonate precipitation from the brines and is given by... 

Addition of chromium, nickel and copper in small concentrations are known to reduce the rate of corrosion in natural, potable, brackish and seawaters. The rate of corrosion is strongly affected by the tendency of cast iron to form scales. The scale forming tendency can be predicted using Langelier s index, discussed earlier in this chapter. 

Langelier index A calculated number used to predict the calcium carbonate (CaCOs) stability of a water that is, whether a water will precipitate, dissolve, or be in equilibrium with calcium carbonate. It is sometimes erroneously assumed that any water that tends to dissolve calcium carbonate will always be corrosive. 

The tendency of water to form scale or cause corrosion is measured by either the Langelier Scaling Index (LSI), which is also called the Saturation Index, or the Ryznar Stability Index (RSI), which is also called the Stability Index (Table 4.2). 

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