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PH PO4 PDF
PH PO4 PDF
phosphate hideout
"Phosphate hideout" and "chemical hideout" are terms used to describe the loss of boiler water
phosphate residual that accompanies this solid phase formation problem.
The phosphate hideout phenomenon can pose a significant chemistry control problem in high
pressure boilers that experience load v ariations.
Typically , phosphate tends to "disappear" as load (steaming rate load) is increased towards
maximum. The pH will also v ary , usually in an upward direction, although one would expect that the
change in pH would be consistent with the change in Na:PO4 ratio of the solution.
The upward trend in pH may be explained by an interaction between phosphate and magnetite that
is also k nown to exist. Just as phosphate disappears with increasing load, so does it reappear with
decreasing load, with concurrent impact on the sy stem pH. Dissolution of the solid phase occurs as
load is reduced.
Historically , "hide-out" had been regarded as an operating nuisance, which continually needed
additions of tri-, di-, and mono-sodium phosphates to k eep the boiler water in the CPT control range.
Howev er, it has been recognized recently that serious corrosion (termed "acid phosphate corrosion")
can result when these chemicals are added to boilers where "hide-out" and deposition are occurring.
The acid phosphate corrosion also prompted Babcock & Wilcox to issue a serv ice bulletin warning all
utility customers of a potential chemistry control problem when using mono-sodium phosphate that
could lead to serious furnace tube corrosion.
Phosphate "hide-out" is characterized by the retention of phosphate in the boiler during conditions of
high load, and its subsequent release when the load is reduced. Various studies of the pure sodium
phosphate water phase diagram suggest that "hide-out" is caused by the precipitation of sodium
phosphate phases at local hot spots and under deposits.
Very high concentrations of phosphate accompanied by extreme pH excursions, may arise from in
congruent precipitation reactions at local sites when "hide-out" tak es place.
The periods associated with sev ere pH depressions often correspond to times when the applied strain
is the highest for corrosion fatigue at v arious locations throughout the boiler.
Coordinated pH-phosphate control was introduced in 1942 as a method of protecting boiler tubes
from "caustic embrittlement," as well as protection from the effects of condenser in-leak age,
primarily water hardness contaminants.
Boiler sy stems containing copper alloy s should hav e a condensate/feedwater pH within the range of
8.8 - 9.2. A ll-steel boiler sy stems are best protected when the condensate/feedwater pH is within the
9.2 - 9.6 range.
A compromise condensate/feedwater pH control range of 8.8 to 9.2 is usually established where both
metals are present.
The basis of a phosphate- pH control is that sodium phosphates are pH buffers.
The addition of phosphoric acid or any one of the orthophosphates to water produces a hydroly sis
reaction that y ields phosphate ions and hy drogen ions, sodium ions, hydroxide ions or combinations,
while caustic hydroly zes to sodium and hydroxide ions.
Within a pH range of from about 9 to about 10.5 the distribution of the different ionic species of
phosphate is at most 1 or 2 % of the mono- or tribasic phosphate ions, while the dibasic hydrogen
phosphate ion, HPO4-2, is more than 98% present.
Thus substantially all phosphates that are added to water within that pH range will hydroly ze to the
dibasic ion., and Tribasic sodium phosphate will hydroly se releasing sodium hydroxide.
• Thus, one mole of trisodium phosphate will increase boiler water pH equiv alent to the
addition of one mole sodium hy droxide.
• Dibasic sodium phosphate hydroly sis has little or no effect on pH
• Monobasic sodium phosphate dissociates to the dibasic form; thus, a one mole addition of
monosodium phosphate is capable of neutralizing one mole of sodium hydroxide or one mole
of trisodium phosphate.