The Kinetics and Mechanism of Formation of Calcium Sulfate Scale Minerals—The Influence of Inhibitors” GEORGE H. NANCOLLAS, WESLEY WHITE, FELIX TSAI, and LARRY MASLOW* Abstract [A seeded growth method has been used to study the kinetics of crystallization of calcium sulfate ‘iydrate at various temperatures and at ionic strengths up to 0.6M. Under all conditions, the rate of reaction is proportional to the square of the relative supersaturation and is controlled by a surface process, The same kinetics are applicable for the growth of calcium sulfate hemihydrate at temperatures above 110 C. The organic phosphonates effectively retard scale formation, and diethylenetriaminepenta (methylenephosphonic acid), when present at a concentration as low as 107M, completely inhibits the growth of calicum sulfate hemihydrate at 120 C. By assuming that the inhibitor molecules are adsorbed on growth sites on the surface of the crystals, the inhibition can be interpreted in terms of a simple Langmuir adsorption isotherm, Fouling of heat transfer surfaces by mineral salts is a major problem in desalination evaporators. The scales reduce the heat transfer efficiency and increase the cost of production of potable water.! Although successful methods have been dovised for the control of “low temperature” scales such as calcium carbonate and magnesium hydroxide, the development of economical and reliable methods for eliminating persistent, pH insensitive, calcium sulfate nucleation, ‘and erystal growth it @ more difficult problem.’ Besides its importance in the field of desalination technology, calicum sulfate formation is also of considerable interest to the geochemist® and petroleum engineer.” In attempts to control the extent of scale formation there are two general approaches: modification of the crystal morphology so that the solids resist packing together as hard destructive scale but rather remain as a sludge which can be swept away by the liquid phase contacting the surface, and the addition of substances which will act as crystallization inhibitors to slow down oF prevent the nucleation and subsequent growth of scale deposits. Calcium sulfete poses a particularly serious problem because of its limited solubility and the decrease in solubility of all the hydrate forms with increasing temperature. In addition, transitions may take place between these hydrates which may be stable, metastable or unstable depending upon the temperature. In order to be able to lunderstand and control the formation of scale, it is therefore important to have kinetic information concerning not only the precipitation of the individual phases but also the mechanisms of the phase transformations which may take place. In the practical case of the desalination of sea water by evaporative distillation, itis desirable to operate at temperatures above 90 C since this improves plant performance and thereby the economic attractiveness. How: lever, at these temperatures, many common additives which are used ‘a scale inhibitors decompose, In addition, the scale composition changes with temperature. It is therefore necessary to develop specific additives which are stable at temperatures above 100 C. ‘Many previous studies of the crystallization of calcium sulfate have employed spontaneous precipitation techniques for growth characterization in the presence and absence of additives. Relatively concentrated solutions containing the lattice ions are ‘mixed together, and the extent of precipitation is followed by monitoring the concentrations of the resulting solution, Although “Submitted for publication October, 1978; revised December, 1978. “Chemistry Department, State University of New York at Buffalo, Buffalo, New York. attempts are made to use reproducible methods of mixing, the ‘concentrations used in these studies have usually been considerably higher than those of interest in the field in order to yield large and ‘measurable concentration changes upon precipitation, The inter- pretation of the results of such experiments is made difficult by the fact that in some cases, the nature of the solid phase which separates is dependent upon the concentrations of the ions in the prec itation medium.?"!° An additional problem in the kinetic inter- pretation of spontaneous precipitation’ studies is that it is not possible to determine whether erystal nucleation and growth occur simultaneously of consecutively. There are probably no systems that are entirely free from dust or other foreign particles which can act as sites for the formation of nuclei of the precipitating phase. The attainment of “homogenous” nucleation conditions, on which the interpretation of spontaneous precipitation experiments is bated, is therefore very difficult even when extreme precautions are taken to ‘exclude foreign particles from the solutions. Frequently, the results of spontaneous precipitation experi: ments are interpreted in terms of equilibrium solubility products, ‘assuming that the driving force for reaction is purely thermo: dynamic in origin, Often, the effects of ionic strength are entirely ignored, and thermodynamic solubility products are used indiscrim= inately without introducing corrections for the activity coefficients under, the conditions of the experiments. It is now well estab- lished** that kinetic factors are of considerable importance in determining the nature of the phase which will separate from solution. Thus, under certain conditions of ionic strength or of temperature, the initially precipitating phase may be thermo: dynamically unstable and may transform to the stable phase during the course of the reaction.?""” Often the initial, kinetically favored, phase will persist for long periods, showing little tendency to transform to that predicted thermodynamically. Arguments, bated ‘upon the solubility of the latter phase will therefore by incorrect. In view of the importance, outlined above, of kinetic factors of the growth and dissolution of crystals, our own work has been concerned with studies.of the growth of seed crystals from stable supersaturated solution. Unlike the results of spontancous precip itation experiments, such studies are highly reproducible, The effects of factors such as ionic strength, temperature, super saturation and the effectiveness of corrosion inhibitors may ther fore be studied quantitatively. In addition, the influence of the nature of the seed crystal phase and morphology upon the subsequent growth reaction may be investigated. Moreover, seeded 0010-9312/79/000099/$3.00/0 304 © 1979, National Association of Corrosion Engineers CORROSION-NACEFIGURE 1 — Exp. C38. A typical calcium sulfate dihydrate growth run at 70 C. Plot of total molar calcium concen. tration against time. Seed cone. = 0.41 gt”, seed B. Inti Vol. 1.00 tite, crystal growth processes are probably better models than are spontaneous precipitation studies for corrosion reactions in which the solid phase is formed heterogeneously, either on a foreign substrate or on crystals already present. In this paper, the laboratory methods which have been used for studies of the kinetics of crystallization of the calcium sulfate hydrates will be described. The reactions have been studied at various temperatures and at ionic strength values up to 0.6M “conditions simulating those found in the field, In addition, the effects of corrosion inhibitors such as the organic phosphonates ‘upon the crystallization reactions will be discussed Experimental Grade A glassware and reagent grade chemicals were used; the phosphonate additives were kindly donated by Dr. T. King, Monsanto Chemicals. Solutions were prepared from doubly distilled ‘water. Calcium sulfate dihydrate seed crystals were prepared by the ‘dropwise addition of 500 ml. of 0.2M calicurm chloride solution to 500 mL of 0,2M sodium sulfate solution at 70 C.'5 The crystals were washed repeatedly until free from chloride and were aged for at least 1 month before use. For experiments at temperatures up to 70 C, the seeds were added to the stable supersaturated solutions in the form of a filtration, washing with ethanol, and drying at 60 C. ‘The plate like monoclinic erystals had an average length of 100 ym, Width of 25 jum, thickness of 5 jum, and analyzed as calcium sulfate dihydrate, Calcium sulfate aheminydrate seed crystals were pr pared by collecting the material precipitated from calcium sulfate supersaturated solutions maintained for at least 12 hours at 130 C in an autoclave. The crystals were separated by filtration through a 0.22 um Millipore filter (Millipore Corp., Bedford, Massachusetts) wathed with anhydrous ethanol and stored over dessicant. They showed a hexagonal needia like form and analyzed [chemical (£ 0.5%) and X-ray ponder diffraction] a the hemihydrate, In erystal growth studies at temperatures below 70 C, stable supersaturated solutions of calicum sulfate were prepared by mixing calcium chloride and sodium sulfate solutions.'® At higher tempera tures, 2 specially designed autoclave was used which enabled the sampling of both the solution and solid phases during the crystallization raactions.'®"7 In these experiments, stable super saturated solutions of calcium sulfate were prepared by dissolving calcium sulfate hemihydrate in double distilad water at room temperature, filtering (Millipore, 0.22 lm), diluting to the desired concentration, followed finally by raising to the desired tempera ture. Stability of the supersaturated solutions was verified by the constancy of total calcium concentratian in solution for at least 1 hour before the start of each experiment. Crystal growth was initiated in the stable supersaturated solutions by the rapid addition of seed crystals. Total calcium concentration changes in solution accompanying calcium sulfate crystal growth were followed by removing a filtered sample, cooling to 100m temperature it necessary), and titrating with EDTA solution using murexide as indicator ( 0.5%). In addition, the grown solid phases were Vol. 35, No. 7, July, 1979 tra} ° 7 we *o Time in min FIGURE 2 ~ Plot of the integrated rate law for exp. C38. characterized by X-ray powder diffraction, and by optical and scanning electron microscopy. Results and Discussion Calciam Sulfate Dihydrate Crystal Growth ‘The crystallization of calcium sulfate dihydrate from super: saturated solutions containing equivalent concentrations of lattice ions, has been shown to follow the rate law given by Equation ayes aren oy Es o in which T is the total molar calcium ion (or total calcium sulfate) concentration at time t, To the equilibrium solubility value, t the time in minutes, k the rate constant, and s is @ function of the number of available growth sites present in the added seed crystals, This work was done at relatively low concentrations, and since ionic strength is an important factor in the field, @ number of experiments have been made at ‘onic strenghts up to 0.60M, maintained by the ‘addition of sodium chloride to the calcium sulfate supersaturated solutions at 70 C, The experimental results are summarized in Table 4, Typical plots of T against time in Figure 1 show that the added seed crystals begin to grow immediately upon introduction into the supersaturated solution; there is no induction effect. At higher soed concentrations, and lower degrees of supersaturation, it is well known that the normal crystal growth is preceded by an induction period during which secondary nucleation takes place at the cerystal/solution intertace.'* Typical plots of the integrated form of Equation (1) are shown in Figure 2 and in Table 1 are given the rate constants expressed as 1? mole! minute! (g seed)", It is interesting to note that Equation (1) satisfactorily represents the rate data at all ionic strengths investigated and that the rate Constants are independent of ionie strength. In addition, the rates of crystallization were found to be independent of the stirring rate, in ‘agreement with the results of experiments at low concentration.’ The evidence again points to an interfacial rate controlling process for the crystallization of calcium sulfate dihydrate rather than diffusion of lattice ions to the solid/liquid interface, The thermo dynamic solubility product (Kgp) was calculated from Equation 2. 305TABLE 1 — Calcium Sulfate Dihydrate Crystal Growth at Various lonic Strengths Exp. (1) Seed Added?) Initial T Nac Initia tonic ks k Apparent Kp?) Number 10° M at Strength, M1 mole"! minute! V'mote! g”' minute! 108M oa 22200462 oat a9 ” a 925 as bet Ouest o.200 8 2 a ee aot am at oaco ‘6 % io cae 331 ozo at o.oo 2 %s 8 ea aaa asa at Osco 4 28 as en tte oaaez at o.sc0 ‘ % 807 Gh120-28(4) 1.08 ° 012 0.043 80 660 12 Gh120.29) 1.07 ° 012 0.043 86 710 1.20 ramps, 70 © Csr wie nome ree of 0.10033" Ka ea") (SORT Temperature, 120 C, calcium sulfate avhemihydrate. Kap ("1 (8081 4 @ in which fis the activity coefficient of a divalent ion, The steady rise in the apparent Ksp in Table, 1 is probably due to the Jnadequacy of the Davies equation’® to calculate the activity coefficients (f2) above an ionic strength of 0.2M. It is important t0 note that the solubility in grams per liter Is greatly increased in ‘going from fresh water to more concentrated brine. Calcium Sulfate Hemihydrate Crystal Growth ‘The growth of the dihydrate seed crystals from supersaturated solutions at temperatures where this phase is thermodynamically stable has been shown to follow the rate Equation (1) involving a surface controlled rate determining step.'® These studies have been extended to temperatures at which transformation to hemihydrate ‘occurs, conditions under which the dihydrate is the thermo. dynamically unstable phase.'”*!® The seeded growth of calcium sulfate dihydrate from room temperature to 105 C shows no evidence of transformation to the anhydrous form despite the fect that this is the thermodynamically more stable phase between 60 and 105 C. It i quite clear that kinetic factors are considerably more important in determining the phase which separates under these conditions, During the erystallization experiments at elevated temperatures, the mass of solid grown on the seed crystals is as much as three times the weight of inoculating seed. In spite of this appreciable increase in surface area, Equation (1) satisfactorily describes the growth process with a single s value. This evidence suggests that, at in @ number of other erystal growth systems! ! growth is confined to the kinks and screw dislocations initially present on the added seed crystals. Near the hydrate phase transition temperature of 105 C, the dihydrate crystals transform to the heminydrate, and the system approaches the hemihydrate solubility value.'® The formation of hemihydrate appears to involve 1 secondary nucleation mechanism with collision breeding of Giheminyarate nuclei followed by concomitant dihydrate dis solution and heminydrate growth, ‘A number of experiments have been made of the growth of calcium sulfate ahemihydrate seed crystals {rom stable super saturated solutions at temperatures above 110 C. Typical experi- ‘mental conditions at 120 C ate included in Table 1, and in order to correct for the gradually increasing solid/solution ratio os samples were removed for analysis, an additional volume correction, Equation (3), was introduced into the kinetic rate Equation (1). vat vod = ks(TTo!? a In Equation (3), V and Vj are the volumes of solution in the autoclave at time (t) and zero time respectively, and s is again expressed as the weight of seed crystals per unit volume of reaction ‘mixture. Plots of total calcium concentration against time are shown 306 Tx10! 0 20 time in ia 30 FIGURE 3 — Total calcium as a function of time for hheminydrate grawth at 120 C. Initial vol = 0.85 liters. Seed cone, = 0.121 in Figure 3. In Figure 4, the linearity with slope 2.0 * 0.1, on plotting log [-{V/Vi) [dT/dt)] against log (T-Tol confirms that Equation (3) satisfactorily represents the crystallization rate of the cehemninydrate as well at the dihydrate. Plots of the rate of crystallization against (T-To]? are shown in Figure 5. These dota, together with the observed independence of the rate of crystal lization upon the rate of stirring again point t0 a surface conteolled process for the crystallization of calcium sulfate achemihydrate Inhibitors Recently, there has been an increasing interest in the applica tion of phosphonates af crystallization inhibitors, sinew these are highly efficient in preventing the nucleation and crystallization of many inorganic salts,'*?9 The main advantage in using phos phonates lies in thair excellent thermal stability. In a previous study." it was shown that in their influence upon the rate of crystallization of calicum sulfate dihydrate at 25 C, the phos: CORROSION-NACEmoa RHF 40] Fry 38 35 mto4 (TT FIGURE 4 ~ A plot of -log [-V/Vj] (AT/dt) against -1og (T-T9). The straight line confirms the functional form of Equation (3) and the slope of the line confirms a second order rate law. Hemihydrate growth at 120 C. 1489) lot of V/Vj) (dT/dt) versus (T-T9)? showing the fit of Equation (3) for hemihydrate growth at 120 C in the presence of DENPMP. Exp. Gh 120 curve 1; B18, 2; 827, 3; B24, 4;826, 5. pPhonates can be divided into three general categories: (1) hydroxy. ethylidene, 1-diphosphonic acid which has only asmall effect on the rate of growth, (2) nitritotri (methylenephosphonic acid) which markedly retards the precipitation but which does not completely Inhibit the reaction even when present at relatively large con: centration, and (3) phosphonates such a N,\,N'N’ ethylene diamminetetra (methylenephosphonic acid and N.N,N'N' triethylene diaminetetra (methylenephosphonic acid) which, in trace amounts completely inhibit the growth of calcium sulfate dihydrate, It has been found?* that for category (3) inhibitors, after well defined Vol. 35, No. 7, July, 1979 FIGURE 6 ~ Growth curves of CaSO, hemihydrate at 120 € in the presence of DENPMP. Exp. Gh 120, curve 1; B18, 2; 827, 3; 824, 4; 826, 5; 821, 6. induction periods in the crystallization reaction, growth of the seed crystals may take place at a rate comparable with that observed in the absence of inhibitors suggesting that the additives are incorp- rated into the developing crystals In the present study, the effect of another multidentate phosphonate, diethylenetriaminepenta (methylenephosphonic acid), DENPMP, upon the rate of growth of calcium sulfate c-hemihydrate seed crystals has been studied at 120 C in an autoclave apparatus.’ * The results of the experiments are shown in Figure 6 and summarized in Table 2. It can be seen that the reaction is completely inhibited at a DENPMP concentration as low as 1.35 x "FM. Plots of the rate Equation (3) shown in Figure 5 confirm the validity of @ second order Kinetics, not only in pure solution, but also in the presence of additive. The rate constant for erystal growth, (k} in pure solution is rapidly reduced to k’ as the concentration of DENPMP increates as is seen in Figure 7. If it ie ‘aszumed that the inhibitor moleculet are adsorbed on growth sites fon the surface of the growing crystals, their presence will prevent deposition of lattice ions near these sites, The relative reduction in the second order rate constant for erystal growth from its value in pure solution may be used at a measure of the extent af adsorption fof inhibitor for which a simple Langmuir isotherm may be applied." The linearity of a plot of k/lk-k’) against [DENPMP] —! shown in Figure 8 indicates that the Langmuir isotherm satis: factorily described the marked inhibiting effect of OENPMP, The phosphonate shows appreciable inhibition of crystallization at concentrations as low as 1.35 x 10°7M (Table 2), while the initial calcium ion concentrations were as high as 1x 107M. This indicates that the complexing of calcium ion by inhibitor molecules is unimportant and that the number of active growth sites on the surface of the hemihydrate crystals is relatively small as was found in the cate of calcium sulfate dihydrate. It is quite likely that the ism is also applicable for the crystallization screw dislocation mech: of the hemiydrate Acknowledgments Acknowledgment is made to the Donors of the Petroleum Research Fund, administered by the American Chemical Society for partial support of this work. We also thank the National Science Foundation for a supporting grant (ENG 74:15486), 307TABLE 2 — The Effect of DENPMP upon Crystal Growth of Calcium Sulfat Calcium Molar Concentration 1.08 x 107M. (DENPMP] Exp. Number 108M. Gh 120 ° B18 1.35 B27 270 B24 5.20 8 26 6.70 B2t 13.50 Hemihydrate at 120C kek)" tOENPMP]“? a) 107M? 157 14 124 37 107 19 11.06 15 1100 07 Notes: k’ = the measured rate constant with DENPMP, and without DENPMP. ‘the rate constant 100] FIGURE 7 — The decrease in the kinetic rate constant with increasing DENPMP concentration. Hemihydrate 1206. owth at References 1. K. S. Spiegler. Salt Water Purification, John Wiley and Sons, Inc., New York, Chapter 4 (1962). 2. W. ‘Stumm and J. J. Morgan. Aquatic Chemistry, Wiley- Interscience, New York (1870), 3. 0. J, G, Vetter and R. C. Phillips. J. Petroleum Tech.,p. 1299 (1970), 4, E.R, McCartney and A, E. Alexander. J. Colloid Sci., Vol. 13, p. 383 (1958) 5. J E, Crawford, E. P. Crematy, and A. E, Alexander. Australian ‘J. Chem., Vol. 21, p. 1067 (1968). 6, C,H. Nestle. J. Colloid Sci., Vol. 26, p. 10 (1968). 7. 8, R. Smith and A, E. Alexander. J. Colloid Interface Sci 34, p.81 (1970). 8. B.A. Smith and F, Sweet, J. Colloid Interface Sci, Vol. 97, p. 612 (1971) 9. G. H. Nancollas and B. Tomazic. J. Phys. Chem., Vol. 78, p. 2218 (1974), B. Tomazic and G. H. Nancollas. J, Colloid Interface Sci., Vol 50, p. 451 (1975). 11. G.H. Nancolles and N, Purdie. Quart. Rev., London, Vol. 18, p. 1 (1964), Vol 10. 4 wrens) 10) > * [oenrae}-1107 FIGURE 8 — A Langmuir isotherm plot for hemihydrate growth in the presones of DENPMP at 120 C. 12. 8. T. Liv and G. H. Nancollas. Desalination, Vol. (1973), 13. C, W. Davies and G. H. Nancollas, Trans. Faraday Soc., Vol. 51, p, 818, 823 (1956). 14, J. R, Campbell and G. H, Nancollas. J. Phys. Cher., Vol. 73, p 1735 (1969) 18. S. T. Livand G. H, Nancollas. J. Crystal Growth, Vol. 6, p. 281 (1970) 16. C.W. Davies. lon Association, Butterworths, London (1962) 17. G. H, Nancollat, M. M, Reddy, and F. Tsai. J. Phys. & (Sci Instr), Vol. 5, p. 1186 (1972). 418. G. H. Noncollas, M. M, Reddy, and F. Tsai. J. Crystal Growth, Vol. 20, p. 125 (1873). 19. 7. M, King, 158th National Meeting of the American Chemical Society, New York, Abstract No. NATR 55 (1969) September. V. J, Vetter, J. Petrol. Technol., p. 997 (1972) M.D. Francis. Calcif. Tiss, Res., Vol. 3, p. 151 (1969) J. L. Meyer and G. H. Naneollas. Calcif. Tiss. Res., Vol. 19, p. 259 (1973). 12, p. 75 20. 21 2. 23. G. H, Nancollas and G. L. Gardner. J. Crystal Growth, Vol. 21, 1.267 (1974), 24, S. T. Liv and G,H, Nancollas, J, Colloid Interface Sci, Vol. 44, . 422 (1973) 25. S.T. Liv and G,H, Nancolla, J, Colloid Interface Sci, Vol. 62, p. 893 (1975) 308 CORROSION-NACE