Patras
P.O. Box 1414, GR 26500 Patras, GREECE
Abstract
Phosphorus recovery from wastewater is determined from the transfer of
aqueous phosphate species into a solid form.
adsorption at the active growth sites. The relative effect of various additives
may be evaluated through the appropriate modeling of the adsorption process.
The case of L-serine is presented which even though is characterized by low
affinity for the hydroxyapatite substrate caused significant reduction of the
crystal growth rate.
1. Introduction
phosphate precipitation, the consensus is that the chemistry of the aqueous phase from
which precipitation takes place is of paramount importance.
Model studies are needed for the assessment of the conditions most appropriate for
the removal and / or recovery of phosphorus from aqueous solutions in the form of
calcium phosphate salts. These studies however should be based on accurate
thermodynamic considerations which may be used next as guides for the appropriate
kinetics experiments. In the present paper an overview of the thermodynamics and
kinetics investigations in aqueous systems of calcium phosphate.
temperature
increase
contribute
to
the
solution
supersaturation
development because the sparingly soluble calcium phosphate salts have reverse
solubility. Following the establishment of supersaturation nucleation takes place.
Once the nuclei exceed a critical size, they grow further in the crystal growth proves
which takes place on the active growth sites of the crystallites. Depending on the
solution supersaturation, four well defined regions may be distinguished for the
calcium phosphate system. These regions are shown in figure 1. As may be seen the
driving force is the solution supersaturations, S, defined as:
S=
IAP
K 0s
(1)
where IAP is the ion activity product of the salt considered and K 0s the respective
thermodynamic solubility product.
Total Ca lcium / M
10-2
DCPA
DCPD
10-3
OCP
TCP
10-4
HAP
10-5
4
10
pH
solutions supersaturated with respect to calcium phosphate, but the precipitation takes
place past the lapse of measurable induction times, following the establishment of the
solution supersaturations.
supersaturated solutions, which are stable. In these solutions precipitation does not
take place, unless they are seeded either with calcium phosphate seed crystals or with
substrates which may function as templates for the selective overgrowth of calcium
phosphates. The lower limit of this supersaturation range is the solubility of the
calcium phosphate considered (S=1). Below this limit, dissolution takes place. It is
thus reported that for pH 7.40 and a molar ratio of total calcium /total phosphate
concentration equal to 1.66, at calcium concentrations of 10 mM spontaneous
precipitation takes place and between 3 10 mM the precipitation takes place past the
lapse of induction times. Below 3 mM the supersaturated solutions are stable for long
periods of time [2].
supersaturated solutions an unstable precursor phase has been reported to form. This
phase is characterized by the absence of peaks in the powder x-ray diffraction pattern
and is known as the amorphous calcium phosphate (ACP). The composition of ACP
appears to depend upon the precipitation conditions and is usually formed in
supersaturated solutions at pH>7.0 [3-6]. In slightly acidic calcium phosphate
solutions the monoclinic DCPD forms [7-9]. OCP is formed by the hydrolysis of
DCPD in solutions of pH 5-6 and may also be precipitates heterogeneously upon TCP
[10,11]. HAP is the thermodynamically most stable phase and often when precipitated
in the presence of foreign ions substitutions calcium, phosphate and / or hydroxyls by
some of these ions take place. Thus, substitutions of OH- by F- or Cl- ions, of the
phosphate by sulfate and carbonate and of the calcium by Sr2+, Mg2+ and Na+ ions
have been reported [12-16]. A considerable amount of the work done for the
identification of calcium phosphate minerals which precipitates spontaneously has
been based on the stoichiometric molar ratio of calcium to phosphate calculated from
the respective changes in the solutions. This ratio has been found in several cases to
be 1.450.05 which is considerably lower than the value of 1.67 corresponding to
HAP which is generally implied as the precipitating mineral. A number of different
precursor phases have been postulated to form including TCP [17-19], OCP [19, 20]
and DCPD [21].
3.
Thermodynamics
mineral
phases.
and
kinetics
of
Experimental
the
formation
methods
for
of
the
deviation of a dissolved salt from its equilibrium value. In figure 2 a typical solubility
diagram for a sparingly soluble salt of inverse solubility is shown. The solid line
corresponds to equilibrium. At a point A the solute is in equilibrium with the
corresponding solid salt. Any deviation from this equilibrium position may be
effected either isothermally (line AB), at constant solute concentration, increasing the
solution temperature (AC),
cause acts as e.g. the introduction of seed crystals of the salt corresponding to the
supersaturated solution.
Labile
Concentration
D
A
Metastable
Stable
Temperature
Figure 2. Solubility- Super solubility diagrams of a sparingly soluble salt with inverse
solubility.
are quite different from salt to salt and as a rule, the degree of supersaturation needed
for a sparingly soluble salt is orders of magnitude higher than the corresponding value
for a soluble salt. Quantitatively, as already mentioned in equation (1), supersaturation
for sparingly soluble salts M+A- is defined as [23]:
(
(
1 /
) ( )
) ( )
Mm+
S=
Mm+
IP
= o
Ks
1 /
[2]
often
an
induction
time
elapses
between
the
achievement
of
supersaturation and the detection of the formation of the first crystals. This time,
defined as the induction time, , is considered to correspond to the time needed for the
development of supercritical nuclei. The induction time is inversely proportional to
the rate of nucleation and according to the classical nucleation theory the following
relationship may be written [24]:
log = A +
B 3s
[3]
( 2.303kT) log S
be
easily
applied
to
the
formation
of
deposits
formed
on
implants.
In
this
case,
Rg =
1 dm
A dt
[4]
Where m is the number of moles of the solid deposited on a substrate in contact with
the supersaturated solution, e.g. seed crystals, or the surface of the implant, and A, the
surface area of the substrate.
The rate laws used to express the dependence of the rates as a function of the
solution supersaturation provide mechanistic information for the mechanism of the
formation of the mineral salt. At a microscopic scale and in analogy with the
mechanism of crystal growth in the vapor phase [25], the sequence of steps followed
for the growth of crystals are shown in figure 2:
3
2
Figure 3: Model for the steps involved in the process of crystal growth of the
supercritical nuclei
The steps involved in the crystal growth of the supercritical nuclei are as follows:
(i) Transport of lattice ions to the surface by convection ( step 1)
(ii) Transport of the lattice ions to the crystal surface by diffusion (step 1).
(iii) Adsorption at a step representing the emergence of a lattice dislocation at the
crystal surface (step 2).
(iv) Migration along the step, integration at a kink site on the step and partial or total
dehydration of the ions (step 3).
The rate of crystallization can be expressed in terms of the simple semiempirical
kinetics equation:
R g = k g f (S) n
[5]
where kg is the rate constant for crystal growth, f(S) a function of the total number of
the available growth sites , n the apparent order of the crystal growth process and
R d = kd
[6]
kd =
DC
[7]
where D is the mean diffusion coefficient of the lattice ions in solution, the molar
volume of the crystalline material, C the solubility of the precipitating phase and
the thickness of the diffusion layer at the crystal surface [26-28].
From the mechanistic point of view it is possible to interpret kinetics data on
the basis of theoretical models the most important of which include adsorption and
diffusion-reaction. The concept of crystal growth proceeding on the basis of an
adsorbed monolayer of solute atoms, molecules or ion clusters was first suggested by
Volmer [29]. Through this monolayer it is possible to exchange ions or molecules
between the bulk solution and the crystal surface The rate in this case is [28]:
Rg = k ad
[8]
[9]
In equation (27),
a is the jump distance and ad the jump frequency of an ion into the
adsorption layer.
4.Kinetics
measurements
hydroxyapatite
in
for
the
supersaturated
precipitation
calcium
of
phosphate
sites).
during
the
precipitation
cannot
provide
accurate
The presence of an
L-
serine
in
contains
ionizable
groups
typically
found
According to
equation (2):
G =
Rg T
ln
IP
K 0s
[10]
In Eq. [10] IP is the ion activity product: (Ca2+)5 (PO4 3-)3 (OH-), K 0s its solubility
product, the number of ions (=9 for HAP), Rg the gas constant and T the absolute
temperature. The ratio IP/ K 0s represents the degree of supersaturation, , and was
computed by the computer code HYDRAQL [30] which is a free energy minimization
program taking into account all equilibria in the solution, mass balance and
electroneutrality conditions. The initial solution conditions and the initial rates of
HAP formation obtained, R, are summarized in Table 1. The experimental conditions
were selected so that the only phase which may be formed is HAP . This was verified
by the constancy of solution composition throughout the precipitation process.
In the absence of any inhibitor, the growth rate as a function of the solution
supersaturation was found to exhibit parabolic dependence, as may be seen in figure
4.
2.00 10-7
1.50 10-7
1.00 10-7
5.00 10-8
10
15
20
25
30
Figure 4: Dependence of the rate of crystal growth of HAP on HAP seed crystals at
37C. (n): Present work; (s) ref. 31; (o) ref. 32
The second order dependence suggested that the mechanism of HAP crystal growth is
controlled by surface diffusion of the growth units to the active growth sites.
As may be seen from Table 1, concentrations of L-serine as low as 2.0x10-3 M
resulted in the inhibition of HAP crystal growth. At this concentration the rate of HAP
crystal growth was reduced by ca 25%. The inhibitory activity increased with
increasing L-serine concentration and may be related to: (i) formation of ion pairs
with calcium in the solution, thereby decreasing the driving force, i.e. the degree of
supersaturation for crystal growth, and (ii) to the blocking of crystal growth sites by
adsorption. Calculations were done by introducing in the computer code HYDRAQL
the formation equilibrium of the 1:1 Ca-serine ion pair with its stability constant
(logK=1.43 at 25C) (25), showed that in the case of the maximum concentration of
serine (0.010 M) only 0.6 % of the total calcium contributes in the formation of the
aforementioned ion pair.
concentration range investigated (1x10-3 1x10-2 M) does not affect to any significant
extent the concentration of free Ca2+ ions and therefore the degree of the solution
supersaturation with respect to HAP. Consequently, the inhibitory effect of L-serine
may be ascribed
growth sites.
Cat
Pt
[NaNO3 ]
Dt
10-4 mol
10-4 mol
10-3 mol
10-3 mol
dm-3
dm-3
dm-3
dm-3
1.50
0.90
1.50
0.00
2.51
1.99
0.86
-3.44
8.4
1.50
0.90
1.50
1.00
2.51
1.99
0.86
-3.44
8.4
1.50
0.90
1.50
2.00
2.51
1.99
0.86
-3.44
6.5
1.50
0.90
1.50
3.50
2.51
1.99
0.86
-3.43
4.9
1.50
0.90
1.50
5.00
2.51
1.99
0.87
-3.43
4.3
1.50
0.90
1.50
10.0
2.52
1.99
0.87
-3.42
2.0
R
HAP
10-8 mol/min
m2
Assuming Langmuir type adsorption, according to which the rate of HAP crystal
growth in the presence of the inhibitor, Ri, is given by [33]:
Ri = Ro (1-b)
[11]
where Ro is the crystallization rate in the absence of inhibitors and (0<<1) is the
fraction of the active growth sites occupied by the inhibitor adsorbed onto the HAP
seed crystals. According to the Langmuir isotherm:
1=
In equation 12,
1
1
+K
[12]
i
Ro
1
1
= +
R o R i b bK LCi
[13]
Plots of the right hand side of equation 13 as a function of the inverse of the additive
concentration are expected to be linear. The plot according to equation 13, is shown
in figure 5.
2.60
2.40
R0/(R0-Ri)
2.20
2.00
1.80
1.60
1.40
1.20
1.00
0
50000
100000
150000
1/c i
Figure 5: Kinetic Langmuir-type plot for the effect of the presence of L-serine in the
crystal growth of HAP at 37 C.
In the case of serine, the linear fit of the kinetics data suggested that for the
concentration range investigated, the inhibitory activity of L-serine may be explained
by blocking of the active growth sites by adsorption. From the slope of the straight
line a value of 130 dm3 / mol was obtained for the affinity constant a value which, as
may be seen from the tabulation of similar values shown in table 2 [32], is rather low
in comparison with other, strong inhibitors of the HAP crystal growth.
Table 2: Comparative data for the affinities calculated from kinetics experiments of
the crystal growth of HAP in supersaturated solutions in the presence of the respective
compounds [32]
Inhibitor
107 KL
Sodium pyrophosphate
0.02
1-hydroxyethylidenephosphonic acid
0.13
Mellitic acid
0.16
Citric acid
0.002
1,2-dihydroxy-1,22.16
bis(dihydroxyphosphonyl)ethane
Zn 2+
3.02
1-hydroxyethylidene-1,1-diphosphonic
0.21
acid (EHDP)
The low affinity of HAP for L-serine may be corroborated from the analysis of
the equilibrium adsorption results. Figure 6 illustrates the adsorption isotherm of Lserine onto HAP, obtained experimentally at pH=7.40.3.
60
50
30
-1
/ m mol
-1
40
20
10
0
0
1000
2000
-1
3000
3
C eq / dm mol
4000
-1
1
K
m C eq
[31]
where , m and Ceq represent respectively the surface concentration, the saturated
surface concentration (i.e. the surface concentration of adsorbate corresponding to
monolayer surface coverage), and the equilibrium solution concentration of L-serine..
From the intercept and slope of the linear regression the values 0.16 mol m-2 and 546
dm3 /mol are calculated for m and KL respectively. Although the values of the affinity
constant obtained from the study of the kinetics of precipitation of HAP on the HAP
seed crystals and of the adsorption of serine onto the HAP surface are different, they
are of the same order of magnitude
The results of the present work have shown that it is possible to model calcium
phosphate precipitation processes in complex aqueous media following careful
References
1.Ferguson J.F, Jenkins D. and Eastman J., Calcium Phosphates Precipitation In :
Proceedings of the 44th Annual Conference of the Water Pollution Control Federation
Ser. 5(2) Oct. 4 (1971).
2. Nancollas G.H., Tomson M.B., Battaglia G., Wawrousek H., and Zuckerman M.,
Precipitation
of
Calcium
Phosphates:
The
Influence
of
Tricarboxylic
Acids,
of their alteration in soils. Soil Sci. Amer Proc., 22, 25-32 (1958)
9. DeRooi J.F., Heughebaert J.C. and Nancollas G.H. A pH study of calcium
phosphate seeded precipitation. J. Colloid Interface Science, 100, 350-358 (1984)
10. Brown W.E., Lehr J.R., Smith J.P. and Frazier A.W.
Crystallography of
LeGeros J.P.
Phosphate Minerals, Nriagu J.O., Moore P.B. Eds., Springer Verlag, Berlin
Heidelberg, pp. 351-385 (1984)
pp. 157-187
for
the
computation
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of
chemical
equilibrium
modeling
oxide/solution
of
interface.
ion
adsorption
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report
at
the
No.
306,
in
aqueous
solutions
by
zinc
and
1,2-Dihydroxy-1,2-