Inhibition of Calcite Crystal Growth by Inorganic Phosphate

W I L L I A M A. H O U S E

Freshwater BiologicalAssociation, River Laboratory, East Stoke, Wareham, Dorset BH20 6BB, United Kingdom
Received August 25, 1986; accepted December 19, 1986 The effectof inorganic phosphate on the crystallizationof calcite has been examined using a free-drift seeded growth method at 25C. The kinetic data are interpreted using a mechanistic model and also a parabolicrate law. The effectof phosphate is explainedin terms of the initial formationof two-dimensional nuclei between adsorbedphosphateions on the steps of the crystals.The inhibition capabilityof phosphate is found to be dependent upon the initial degree of supersaturation of the aqueous solution. 1987
Academic Press, Inc.

INTRODUCTION

In a previous paper (1) the adsorption and coprecipitation of inorganic phosphate on calcite was studied in a temperature range of 5 to 35C. The results showed that the amount of phosphate coprecipitated depends on the calcite precipitation rate and the adsorption of phosphate on the growing crystals. Only a fraction of the total adsorbed phosphorus was incorporated in the calcite. Research on a reCRYSTAL GROWTH MODELS circulating experimental stream system (2) has Models describing the crystallization of calshown that at concentrations of inorganic cite from solutions not containing inhibitors phosphate found in natural waters, the complete inhibition of calcite growth can occur. have been examined by House (5) and more The present work was started to investigate recently by Inskeep and Bloom (6). The most the inhibition properties of phosphate during successful models are the mechanistic models seeded calcite growth experiments in calcium of the type postulated by P l u m m e r et aL (7) and Nancollas and Reddy (8). Cassford et al. bicarbonate solutions. Meyer (3) has examined a n u m b e r of in- (9) have applied a mechanistic model derived hibitors of calcite growth which are active at from the theory of P l u m m e r et al. (7) in the very low concentrations (<10 -6 mole din-3). form Reddy (4) has examined in detail the effects dncaTdt = WksaHco~,I 1 - ~a2+ exp/3J, t l l q of trace concentrations of phosphorus-containing anions including orthophosphate. The results indicate that low concentrations of in- where s is the surface area of calcite which i's hibitors are very effective in reducing the nucleated per gram of seed; k is the rate congrowth rate. stant; Wis the mass of seed; all+ and a~+(s) are The inhibition properties are generally as- the hydrogen ion activities in the bulk and sessed from a series of seeded growth experi- surface adsorption layers, respectively;/3 is the ments over a range of inhibitor concentrations. growth affinity defined as 505 0021-9797/87 $3.00
Journal of Colloid and Interface Science, Vol. 119, No. 2, October 1987

No work has been done with calcite to examine how the inhibition is affected by the initial supersaturation of the solution. The present work shows that it is important to consider not only the inhibitor concentration, but also the range of supersaturation over which the inhibitor is expected to remain effective.

Copyright 1987 by Academic Press, Inc. All rights of reproduction in any form reserved.

506

WILLIAM A. HOUSE
= ~ 2x#i/RT = ln[aca~+, aco~-/K~ol,
i

[21

where i denotes the lattice ions, AUg is the change in chemical potential caused by crystallization, and Kso is the solubility product of calcite. The crystallization rate is expressed per gram of seed in terms of the change in the number of moles of total dissolved calcium in the system per unit time, i.e., crystallization rate, G = (dncar/dt)/W. Equation [ 1] is derived on the assumption that the reaction between partially dehydrated [Ca-HCO3] complex or ion pair in the hydrodynamic boundary layer with an adsorbed CO32- ion controls the precipitation rate. The adsorbed layer is assumed to be in dynamic equilibrium with the calcite surface and the concentration of CO2 at the surface is the same as that in the bulk. This implies that neither surface diffusion nor integration of the lattice ions is rate limiting. The value o f s in the precipitation experiments is determined by the surface nucleation on the seed material at the start of the experiment. Reddy and Gaillard (10) have shown that s depends on the seed concentration. However, if the seed concentration is not varied greatly, then it is convenient to express the rate constant as a combination of the "absolute" rate constant, k (unique for a particular material), and the surface area of calcite nucleated per gram of seed, i.e., kl = ks. Previous work has shown that s is not necessarily the same as the specific surface area of the sample (9) because only part of the crystal surface may be nucleated and involved in the growth (1). Unfortunately this means that without a method to determine s, the rate constant, k, cannot be evaluated. As a consequence of this, the measured rate constant, kl, generally varies between different preparations of calcite (9). Another model which has been applied to calcite growth is that due to Davies and Jones (5, 6, 9, 11). This may be written in the form
dnCaT

where S is the supersaturation ratio defined by AN ln/-aCa2+"ac~-/1/2 , [4] where 2x# is the average chemical potential change per ion. The measured rate constant, ~ , also incorporates the parameter s. Equation [3] is equivalent to the parabolic rate law examined by Nielsen (12) and applied to calcite growth by Nielsen and Toft (13). The empirical rate law has been explained by Nielsen (12) on the basis that one of the factors (S - l) comes from the density of kinks on the crystal faces and the other factor is proportional to the net flux per kink of ions from solution onto the crystal (12). The density of kinks on the crystal may be estimated using the BCF theory of growth (14). Nielsen has extended the BCF theory to high supersaturations to find that the density of kink sites is proportional to
Sl/2[1 + (3S)-l/2]-aln S ~ ( S - 1).

[5]

EXPERIMENTAL The experimental details have been described previously (1, 9). In brief, the seeded growth method was used under free-drift conditions. The seed material was the same as that used by Cassford et al. (9). It was calcite as determined by X R D with a nitrogen BET specific surface area of 0.22 m 2 g-J. The reaction was followed automatically using an Apple II microcomputer interfaced with a Radiometer PHM64 meter for pH measurement and Wayne-Kerr B905 ac bridge for conductivity measurements. The experimental procedure was as follows. The Ca(HCO3)2 solutions were prepared from calcium carbonate (AR grade, BDH Chemical, Ltd., Poole, England) dissolved in CO2-rich triple-distilled water (conductivity <0.5 t~S cm-l). The solutions were then adjusted to a calcium concentration of-~2.5 mmole dm -3 and phosphate concentration of between 3 and 12 #moles dm -3 by the addition of between 25 and 100 mm 3 of concentrated KH2PO4.

dt

- Wlcp(S- 1)2,

[31

Journal of Colloid and Interface Science, Vol. 119, No. 2, October 1987

CALCITE GROWTH

507

After temperature equilibration (+_0.002C), the reaction solution was outgassed of CO2 using nitrogen, until a particular pH was attained. After ensuring that the solution was stable for a period of about 30 min, a sample was removed for phosphate analysis and the reaction was seeded with a calcite suspension (60 mg/g of suspension). The reaction was then monitored for about 5 h. The conductivity readings were corrected for KCI leakage from the reference electrode and, together with pH, used to calculate the solution speciation using the method described previously (1). The contribution of phosphate to the conductivity was negligible and not accounted for in the calculations. In a number of experiments, the total phosphate concentration was measured at six times during the reaction. The adsorption of phosphate onto the seed material prior to growth was too small to be measured.
RESULTS AND DISCUSSION

A series of 17 crystallization experiments covering a range of phosphate concentrations

and initial growth affinities, f l i , w e r e monitored. The first 5 experiments were done without the addition of phosphate with the purpose of determining whether the growth rate was dependent on the initial supersaturation. The upper limit of fli in those experiments was determined by the heterogeneous nucleation of calcite onto the glass reaction vessel. Previous results (15) indicated that this was likely to occur with fli > 3.2. The remaining experiments had an average initial phosphate concentration of 3.19 +_0.02, 6.14 +_ 0.09 and 12.46 _+ 0.81 #mole dm -3. The initial phosphate concentrations and growth affinities are listed in Table I. The solutions containing phosphate were all stable at a growth affinity, fli, prior to seed addition. In all experiments the final phosphate concentration was < 1 #mole dm -3 indicating the coprecipitation of phosphate. In experiments 6-12 the coprecipitation rate followed the model proposed previously (1). In the remaining experiments, i.e., 13-17, the coprecipitation was not measured in detail. All solutions containing phosphate were supersaturated

TABLE I Results of the Analysis Using the Mechanistic Model

Initial phosphate concentration (#mole dm -3) 0 v fll 2.21 kl (mole rain-l g-t) 0.0120 (10--6) -(din3 g-t) 3.94

Experiment number 1

2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

0 0 0 0 3.22 3.18 3.18 6.02 6.11 6.19 6.23 12.45 11.65 12.72 13.67 11.79

2.30 2.56 2.79 3.09 3.06 3.08 3.13 3.33 3.34 3.55 3.71 3.43 3.50 3.82 4.14 4.48

0.0133 0.0121 0.0124 0.0126 0.0054 0.0060 0.0091 0.0050 0.0042 0.0076 0.0092 0.0007 0.0014 0.0041 0.0047 0.0068

-0.45 0.62 0.86 2.01 2.28 0.21 0.69 0.30 0.38 1.00 0.88 0.69 1.16 0.89 0.70

4.96 5.24 6.38 6.80 6.65 6.48 6.63 6.83 6.66 6.97 7.22 5,18 3.66 4.75 4,93 5.26

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WILLIAM

A. H O U S E

with respect to calcium hydroxyapatite but undersaturated with respect to octacalcium phosphate. Mechanistic model. The results were first analyzed using Eq. [ 1] by the same method as that described by Cassford et aL (9). This involved dividing the range of 13 applicable to each experiment into 20 equidistant points. A numerical procedure was programmed to obtain an optimum value of k~ which produced the best agreement between the partial pressure of CO2 in equilibrium with the solution (calculated from the conductivity and pH measurements) and the partial pressure of CO2 in the adsorbed layer, Pco2(s). The value of Pco2(s) and the condition that the surface layer is in equilibrium with calcite permitted a value of am(s) to be calculated. The mean sum of squares deviation, 6 = ~zOi=l [P~o~ i 2 -Pco2(s)]/20, together with the calculated rate constants, is listed in Table I. The magnitude and variation in the 6 values for all the experiments suggest that the mechanistic model is just as applicable to the experiments without phosphate as to those containing phosphate at the start. Any changes in the crystallization rate caused by the decreasing phosphate concentration during the experiment are not enough to affect the applicability of the model. However, an important feature of the results in Table I is the effect of /3i on the measured rate constant, kl. As shown in Fig. 1, the experiments without phosphate addition produced a rate constant of 0.0125 ___0.0005 mole min -~ g-1 over a range offli of 2.2-3.1. In the experiments containing phosphate, kl is dependent on both/3i and the initial phosphate concentration as shown in Fig. 1. For experiments 1-5, small variations in the seed concentration do not produce a systematic effect on k~. In some of the experiments at the highest phosphate concentration, the seed mass concentration in the reaction was increased slightly to produce a faster growth rate. If the rate constant, k, is constant for calcite in all the experiments and independent of the initial solution composition, then the depenJournal of Colloid and InterfaceScience, Vol. 119, No. 2, October 1987

E -6

L
~ 4 2 0 2.0

2.4

2.8 3.2 3.6 Initial growth affinity

4.0

4.4

FIG. l. Comparison of the rate constants derived using the mechanisticmodel. The initial phosphate concentrations are (O) 0, (I) 3 #mole dm-3, (0) 6/zmoledm -3, and (A) 13 #mole dm-a. The least-squares lines are shown.

dence of k~ on the initial solution supersaturation must reflect the dependenceof s on/3i. It is then possible to explain these results by assuming that only part of the available calcite surface is nucleated in the presence of phosphate. This view is supported by SEM studies (1) which discovered overgrowth layers not seen on the seed material. If the initial nucleation is so important, then it is possible that the initial phosphate concentration is sufficient to inhibit growth on certain areas of the calcite surface. Such a mechanism would require the two-dimensional nucleation of pure CaCO3 between phosphate ions adsorbed at step positions. The critical radius, re, of such a nucleus is
rc = 3"VmlAU = "r VmlBkT,

[6]

where -y is the surface free energy, Vm is the molecular volume of a growth unit, and Alz is the corresponding chemical potential change caused by the incorporation of a single growth unit into the lattice. The growth unit is taken to be a molecule of CaCO3. Hence the inhibition of nucleation occurs when the surface density of phosphate is such that a critical twodimensional nucleus cannot form on a step. The critical radius may be simply related to the surface density of phosphate, i.e.,
T c 1/2 -=- 2r~

CALCITE GROWTH and

509

Tc \23"Vm]'

_{

[7]

I 113 ~M

where Tc is the critical surface density of all phosphate species. According to this model, the rate constant k is independent of the surface phosphate concentration and a ratio R may be defined

R = kl(Px)/kl(O) = s(Px)/s(O),

[81

12 luM

oL,

where the quantities in brackets refer to the initial concentration of total phosphate, [P]t, in solution. In general, R can be written in terms of a function describing the distribution of phosphate surface densities, i.e., R =

T/ ~mol-2 m

FIG. 2. Estimated distribution of phosphate surface densities derived using Eq. [9].

f?
1

f(T)dr,

[9]

where T~ is the lowest surface density. The range of T extends to T2, the m a x i m u m surface density. Given detailed information about R for T2 >~ T >~ TI it is possible to evaluate f(T). Experiments 6-17 provide a limited range of data for this type of analysis. However, some crude estimate o f f ( T ) may be attempted on the assumption that k~ is a linear function of/~i for a particular initial phosphate concentration. This assumption permits a calculation of T1 and T2 from/3i corresponding to kl(P-r) = 0 and kl(PT) = kl(0), respectively. Until more data concerning variations in the rate constant over a wider range of/3i are available, this interpolation is open to criticism. However, the method does allow estimates of the range of T to be expected from such a mechanism. The distribution functions obtained by linear regression analysis are illustrated in Fig. 2. It is evident that the surface densities calculated by this method are much higher than those derived from the adsorption isotherm analysis at 25C (1). The isotherm analysis produced values of nm/Z of 0.545 umole m -2, where nm is the m a x i m u m adsorption amount and 2 is the specific surface area. This compared with a m a x i m u m surface density of co-

precipitated phosphate of 0.224 tzmole m-2(1). These values may be compared with estimates of the surface density of kink sites using the relationships derived by Nielsen (12) for the kink distance Xo,

Xo = a S - m e x p ( a 2 y / k T ) ,

[10]

where a is the molecular diameter (= Vm/2) 1/3, and the step distance Y0, yo = 4~r[1 +(3S)-1/2]rc. [11]

The kink density (1/XoYo) calculated with -/ = 97 ergs cm -2 (16) varies between approximately 2 X 1016 and 1017 m -2 for/3 between 2 and 5. These densities are much smaller than the surface densities of phosphate shown in Fig. 2, e.g., 2 umole m -2 corresponds to approximately 1.2 X 1018 m -2. Therefore, to produce the necessary density of phosphate needed to inhibit two-dimensional nucleation, adsorption at both kink sites and along steps is essential. The maximum surface density of coprecipitated phosphate of 1.3 X 1017 m -2 corresponding to 0.224 umole m -2 is of the order of the kink site density and suggests that only phosphate adsorbed at kink positions is incorporated into the growing crystals. Parabolic rate law. Previous analysis of precipitation rate data for systems without inhibitors and over a temperature range of 5 to 30C has shown that Eq. [3] produces reasonable agreement at low precipitation rates but fails
Journal of Colloid and Interface Science, Vol. 119, No. 2, October 1987

510

WILLIAM A.

HOUSE

TABLE II at higher rates ca. >5 t~mole dm -3 min -~ (9). The analysis of the data from experiments 1Results of the Analysis Using the Parabolic Rate Law 5 produced similar results and agreement with Initial phosphate the model for rates <40 tzmole min -1 g-I (see Experiment concentration /% Fig. 3). The rate constants are presented in number (#mole dm -3) fli (#mole rain-~ g-~) Table II together with the standard errors from 1 0 2.21 23.52 _+ 1.72 the least-squares lines. 2 0 2.30 17.19 _+ 1.37 The entire data from each experiment may 3 0 2.56 21.27 ___ 1.47 be described by a compound rate law following 4 0 2.79 23.11 + 1.36 a linear dependence at higher supersaturations 5 0 3.09 18.14 + 0.65 6 3.22 3.06 3.40 + 0.54 and becoming parabolic as the rate decreases 7 3.18 3.08 0.33 + 0.05 at lower supersaturations. According to Niel8 3.18 3.13 6.61 + 0 . 1 9 sen (17), the linear region can be associated 9 6.02 3.33 3.95 + 0.04 with an adsorption mechanism when the rate10 6.11 3.34 2.87_+0.12 determining step is the adsorption of a growth 11 6.19 3.55 4.96 + 0.15 12 6.23 3.71 7.46 + 0.05 unit onto the surface. At lower supersatura13 12.45 3.43 0.30 - 0.02 tions, the incorporation of the growth unit into 14 11.65 3.50 0.97 _+ 0.01 the lattice becomes rate limiting and leads to 15 12.72 3.82 4.23 _+ 0.04 the observed parabolic law (12). 16 13.67 4.14 5.63 + 0.09 In contrast, the results obtained in the pres17 11.79 4.48 7.24 _+ 0.36 ence of phosphate produced agreement with the parabolic model with the least-squares lines passing close to the origin. The data from the porates s), is dependent on both the inhibitor experiments with an initial phosphate con- concentration and the initial supersaturation. centration of 6.14 + 0.09 ~moles dm -3 are The fact that the parabolic law is extended shown in Fig. 3 and the rate constants and over a greater range of supersaturation suggests standard errors for all the experiments are in that adsorption is no longer rate limiting. This Table II. The results suggest that the phosphate may be the result of a decrease in the density effects the initial nucleation by a mechanism of advancing ledges on the crystal surfaces similar to that proposed for the mechanistic caused by the presence of phosphate during model. The rate constant, k (which incor- the initial nucleation. The flux of growth units w adsorbing onto the crystal may then be sufficient to make the subsequent incorporation of these units into the lattice the rate-limiting event. The analysis by the mechanistic and paraj'~ 120 bolic models suggests that the concentration of phosphate during growth is not important E 10C in determining the precipitation rate once nu~o cleation has occurred. This is illustrated in ~'~ 6C more detail in Table III Where the ratio of the ~,ks 4o growth rates with and without phosphate (G/ 20 Go) is calculated for experiments 9-12. The G values were obtained from the range of fl in 4 8 12 16 20 [~_q2 experiments 3 and 4. The results produce no consistent trend in the value of G/Go with FIG. 3. Results o f the analysis of experiments 4 and 9 changing phosphate concentrations. The only 12 obtained using the parabolic rate law. Key: ( e ) exp. 4, (A) exp. 9, (111)exp. 10, (IS]) exp. 11, () exp. 12. point which emerges is that there is a trend of

Journal of Colloid and Interface Science, Vol. 119, No. 2, October 1987

CALCITE GROWTH TABLE III Comparison of Growth Rates with and without Phosphate ~ Phosphate concentration (~rnoledrn-3) G (~mole rnin-i g-l)

511

B Experiment 9 2.722 2.337 2.003 1.888 Experiment 10 2.463 2.082 1.863 1.720 Experiment 11 2.717 2.261 2.141 Experiment 12 2.556 2.072 1.858
G = (dnc.T/dt)/W.

G/Go

menced. The mechanistic model describes the precipitation in solutions containing phosphate. The changes in the measured rate constant, kl (=sk), with/3i may reflect variations in the surface density of phosphate initially adsorbed on the seed material.

4.59 3.61 2.49 1.30 3.92 2.81 1.75 0.84 4.18 3.14 1.81 3.49 2.55 1.64

34.20 21.24 13.48 14.52 18.42 12.33 12.01 12.60 41.50 22.68 24.86 45.86 23.70 18.80

(iii) The parabolic rate law is applicable to growth data for solutions containing phosphate. The deviations from the rate law observed at high supersaturations with pure Ca(HCO3)2systems are not observed with solutions containing phosphate. This difference 0.23 is attributed to the effect of phosphate on the 0.23 nucleation of growth on steps at the time of 0.28 0.27 seeding. 0.34 0.30 o.27 0.33
ACKNOWLEDGMENT 0.42 0.35 0.43 0.53 0.44 0.44 I thank the Natural Environmental Research Council, United Kingdom, for supporting this work. REFERENCES
1. House, W. A., and Donaldson, L. J., Colloid lnterface Sci. 112, 309 (1986). 2. House, W. A., Casey, H., and Smith, S., Water Res. 20, 923 (1986). 3. Meyer, H. J., J. Cryst. Growth 66, 639 (1984). 4. Reddy, M. M., J. Cryst. Growth 41,287 (1977). 5. House, W. A., J. Chem. Soc. Faraday Trans. 1 77, 341 (1981). 6. Inskeep, W. P., and Bloom, P. R., Geochim. Cosmochim. Acta 49, 2165 (1985). 7. Plummer, L. N., Wigley, T. M. L., and Parkhurst, Amer. J. Sci. 278, 179 (1978). 8. Nancollas, G. H., and Reddy, M. M., J. Colloid Interface Sci. 37, 824 (1971). 9. Cassford, G. E., House, W. A., and Pethybridge, A. D., J. Chem. Soc. Faraday Trans. 1 79, 1617 (1983). 10. Reddy, M. M., and GaiUard, W. D., J. Colloid InterfaceSci. 80, 171 (1981). 11. Davies, C. W., and Jones, A. L., Trans. Faraday Soc. 51, 812 (1955). 12. Nielsen, A. E., PureAppl. Chem. 53, 2025 (1981). 13. Nielsen, A. E., and Toil, J. M., J. Cryst. Growth 67, 278 (1984). 14. Bennema, P., and Gilmer, G. H., in "Crystal Growth: An Introduction" (P. Hartman, Ed.), p. 263. NorthHolland, Amsterdam, 1973. 15. House, W. A., and Tutton, J. A., J. Cryst. Growth 56, 699 (1982). 16. Sohnel, O., and Mullin, J. W., J. Cryst. Growth 60, 239 (1982). 17. Nielsen, A. E., J. Cryst. Growth 67, 289 (1984). 18. Davey, R. J., J. Cryst. Growth 34, 109 (1976). JournalofColloidandInterfaceScience.Vol. 119,No. 2, October1987

increasing G/Go with increasing /3~. Models describing the effects of inhibitors, such as those proposed by Davey (18) and Koutsoukos et al. (19) in which adsorption of impurities at kinks, steps, or ledges affects the growth rate, are inconsistent with the present results. This is because, according to these models, the step velocity and hence the growth rate depend on the inhibitor concentration during growth.
CONCLUSIONS

It has been shown that inorganic phosphate has an effect on the crystallization kinetics of calcite. In particular, (i) The inhibition of growth depends on both the phosphate concentration and the initial supersaturation of the solution when the seed material is added. (ii) Although phosphate is coprecipitated, the phosphate in solution does not appear to affect the kinetics once growth has com-