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a r t i c l e
i n f o
Article history:
Received 30 January 2014
Received in revised form 15 May 2014
Accepted 15 May 2014
Available online 22 May 2014
Editor: J. Fein
Keywords:
Free energy of activation
Enthalpy of activation
Entropy of activation
EyringPolanyi equation
Calcium carbonate
Calcium sulfate
a b s t r a c t
Calculation of the thermodynamic parameters Eact, H, S and G for the precipitation, crystallization and
dissolution processes of the salts CaCO3 and CaSO4, leads to very important conclusions about the activated
steps and the mechanisms. The G values are almost the same for all the processes at the same temperature, sug2+
and SO2
gesting that the electrostatic forces between the ions Ca2+ and CO2
3 (CaCO3) and Ca
4 (CaSO4) are the
most important factors governing the above processes. The values of H and S differ but the values of G
which refer to the overall transformations are the same and are independent of the various steps that take place
as well as the mechanisms (associative, dissociative). Dehydration and aquation of the ions are revealed by the
values of H and S. The precipitation of the two salts may take place both by a dissociative mechanism
(S N 0) or by an associative mechanism (S b 0). For processes taking place without the need for diffusion
2
1
, whereas when diffusion of
of the ions, (Ca2+, CO2
3 , SO4 ), the free energy of activation is about 85 kJ mol
1
the ions is necessary, an additional amount of ~20 kJ mol is required. This amount is the activation energy for
the diffusion. In the case of CaCO3, a wide range of values is found for H from 66.00 to 162.00 kJ mol1,
and for S from 501.00 to +248.00 J K1 mol1 while the G values cover only a small range from 75 to
90 kJ mol1. Values of 120, 131 and 132 kJ mol1 are reported for cases where retardation is caused due to the
presence of foreign compounds. In the case of CaSO4, a wide range of values is found for H from 6.00 to
122.00 kJ mol1 and for S from 342.00 to +117.00 J K1 mol1 while the G values fall in the narrow
range from 80.00 to 89.00 kJ mol1. A value of 126 kJ mol1 is reported for cases where retardation is caused
due to the presence of foreign compounds. The Eact values vary between 63 and 164 kJ mol1 for CaCO3 and between 8 and 184 kJ mol1 for CaSO4, demonstrating once again that the G value is more realistic, being almost
the same for similar processes. The various small differences for the values of G arise from the different ionic
strengths due to the concentration and charge of the foreign ions affecting the rate constants and thus the activation parameters. The pH also has an effect, as does the nature of the solvent. The very large and very small absolute
values of H and S suggest composite reactions. Composite reactions in the precipitation, crystallization and
dissolution processes are the ones where dehydration takes place (positive values of H and S) followed by
association of the ions (negative values of H and S). The algebraic sum of the relevant H and S values
gives the total value of H and S. Activation energy values reported in the literature for certain cases compared to the values reported in the presence of adducts do not indicate retardation. On the contrary, they suggest
acceleration of the reactions. The use of G instead of the Eact values is more realistic in showing the large retardation effect. The presence of salt, for example NaCl, causes retardation of the crystallization process.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Calcium carbonate (CaCO3) is an important material that occurs in
the natural environment as a constituent of many biological, geological
and ecological systems, while it is also involved in many industrial processes, for example in scale formation. For these reasons, precipitation,
crystallization and dissolution of calcium carbonate in aqueous
Corresponding author.
E-mail address: athpetrou@chem.uoa.gr (A.L. Petrou).
http://dx.doi.org/10.1016/j.chemgeo.2014.05.018
0009-2541/ 2014 Elsevier B.V. All rights reserved.
solutions has attracted the interest of many investigators in a wide variety of elds. Many studies have focused on the problems that are related
to the mechanism of its formation, and the role that various parameters
play in its formation in aqueous solutions has been studied (Koutsoukos
and Kontoyannis, 1984). Thermal decomposition has also been studied
by several investigators and various mechanisms have been reported
(Rajeswara Rao, 1993, and refs. therein).
Calcium sulfate (CaSO4) has also been intensively investigated since
many aspects of its reaction mechanisms remain unanswered
(Klepetsanis et al., 1999). Solution chemistry helps greatly in the
145
arrangement before they can be transformed into the products of the reaction. The specic, transient, arrangement that possesses a denite energy is known as the transition state. The transition state or activated
complex theory postulates that the reaction proceeds through formation of an activated complex that is in equilibrium with the reactants
(Petrou and Economou-Eliopoulos, 2009b; Petrou, 2012), and the rate
constant is given by:
H TS :
The above Eq. (3) is the general form of the Eyring equation or Activated Complex Theory equation, which is also known as EyringPolanyi
equation in chemical kinetics. It relates the reaction rate constant to
temperature and its linear form is:
146
H
Eact RT;
5Table 1
Kinetic data (k, T) and calculated thermodynamic parameters (Eact, H, S, G) for precipitation, crystallization and dissolution of calcium carbonate (CaCO3).
T (K)
1. Precipitation in aqueous solutions
Case (d)
Case (e)
Case (e*)
Case (f)
Case (h)
Case (i)
Case (m)
Case (n)
Carrara marble
Case (n)
Iceland spar
298.15
308.15
318.15
283
298
313
278
298
310
335.7
318.7
302.3
lnk(a)
1
E(b)
act kJ mol
H(c) kJ mol1
S(c) J K1 mol1
G(c) kJ mol1
5.12
4.446
1.485
5.265
3.932
2.318
5.10
4.78
4.483
15.61
16.76
17.91
142.2(c)
155(d)
139.6
177.8
84.8 at 308 K
72.1(c)
71.2(e)
69.7
42.5
82.8
13.52(c)
11.09
246.9
87.13
58.1(c)
46(f)
55.43
210.4
120.2 at 308 K
57.04(c)
57.1(g)
54.5
66.4
75 at 308 K
43.5(c)
43.1 3.8(h)
41.0
135.3
82.7 at 308 K
46.7(c)
28.9(c)
46 4(i)
44.2
26.5
120.3
181.9
81.3
82.5
163.9(c)
161.4
247.6
85.1
63.03(c)
65.52
501.2
88.86
73.6(c)
66 2(k)
71
40.78
58.44
73.7(c)
73 10(k)
71.3
59.75
89.7
34.7(c)
35.1(l)
32.2
233.2
104.0 at 308 K
20.22(c)
(m)
17.5
207.5
81.4 at 308 K
59.1(c)
54 4(n)
56.5
88.9
83.9 at 308 K
45.14(c)
46 4(n)
42.5
145.5
87.3 at 308 K
388.7
130.84
284.4
294.7
298
306.8
315.5
284
293.5
302.1
312.7
298
283
313
298
298
300.5
306
293
298
306
301
312,5
323
283
293
298
1.715
0.759
0.58
0.223
0.621
4.211
3.70
3.158
2.532
3.139
3.758
1.966
2.871
5.952
5.298
4.2
4.001
4.343
5.09
6
7
8
7.97
6.84
6.67
278
293
303
313
323
298
323
353
298
314
328
335
298
314
328
335
276
298
353
276
298
353
12.786
11.564
11.418
10.82
10.68
2.659
1.833
1.386
4.075
2.779
1.871
1.431
5.167
4.382
3.59
3.137
22.384
21.59
21.011
22.76
22.00
21.19
13.72(c)
11.12
383.6
16.1(c)
13.5
131.6
147
Notes to Table 1:
(a) Experimental data in units of T in K and of k in: s1 (cases d, f, k), nm s1 (case g), M1 s1/mg seed l1 (case h), M1 s1/mg seed/100 ml (case i), s1 cm2 (case l), mol m2 s1
(case m), cm s1 (case n), mol m2 s1 (case e), l2 s1 mol1 cm2 (case j, kRS), l2 s1 mol1 mg1(case j, kRM), mol cm2 s1 (case o).
(b) Calculated values.
(c) This work.
(d) Koutsoukos and Kontoyannis, 1984.
(e) Romanek et al., 2011.
(f) Xyla et al., 1991.
(g) Kralj et al., 1990.
(h) Wiechers et al., 1975.
(i) Nancollas and Reddy, 1971.
(j) Hasson et al., 2010.
(k) Rodriguez-Blanco et al., 2011.
(l) Sjoberg, 1976.
(m) Alkattan et al., 1998.
(n) Sjoberg and Rickard, 1984.
(o) Schott et al., 1989.
148
the S values (for explanation see below) gives a small overall negative result. The H value being also the algebraic sum of the H
values of the two processes also has a small value. This value is obviously smaller than the value due to dehydration only [see case (d)]. This
means that, in this case, the association of the ions in the lattice happens
Table 2
Kinetic data (k, T) and calculated thermodynamic parameters (Eact, H, S, G) for precipitation, crystallization and dissolution of calcium sulfate (CaSO4).
lnk(a)
1
E(b)
act kJ mol
H(c) kJ mol1
6.624
4.634
2.534
0.394
4.094
3.401
2.639
2.303
12.3
11.2
10.66
11.354
11.864
12.284
2.6
2.9
3.1
5.113
5.310
5.436
124.3(c)
184 2(d)
121.7
7.497
7.55
7.619
4.656
3.663
3.211
2.885
2.083
2.425
1.099
1.204
2.303
3.75
4.1
4.8
2.554
3.321
4.181
5.053
13.332
11.190
10.131
9.302
2.557
1.799
1.012
2.601
1.752
0.933
19.625
19.113
18.644
18.015
2.55
2.23
1.92
1.52
40.33(c)
65.2(j)
T (K)
283
288
293
298
303
4.358
4.160
3.808
3.381
3.182
S(c) J K1 mol1
116.7
G(c) kJ mol1
85.8 at 308 K
51.62(c)
5171(e)
49
84.6(c)
84.30(f)
81.9
72.2
14.2(c)
(g)
11.5
307.8
106 at 308 K
12.12(c)
30(h)
9.3
242.63
84.03 at 308 K
8.84(c)
3050(i)
6.274
268.45
88.96
37.4
200.7
99 at 308 K
64.75(c)
62.8 2(k)
62.2
66.7
82.8 at 308 K
68.1(c)
52.6(l)
65.41
47.5
80.04 at 308 K
26.4(c)
26.930.7(m)
Average = 28.9
39(c)
66.9 6.3(n)
23.9
201.36
85.92
at 308 K
36.5
157.9
85.12
at 308 K
60.68(c)
62.8(o)
57.93
162.25
107.9
at 308 K
62.79(c)
60.2
67.63
81.03
at 308 K
67.832(c)
64.9(p2)
65.23
51.28
81.03
at 308 K
22.015(c)
13.7623.14(q)
20.39
341.45
125.56
at 308 K
33.9(c)
34 2(r)
31.05
173.83
84.59
44.6(c)
41.8 6.3(s)
42.2
132
82.9 at 308 K
117
(p1)
85.02 at 308 K
104.1 at 308 K
during the activation step, whereas in the case of precipitation [case (d)]
only dehydration occurs during the activation step. The G is approximately 75 kJ mol1 at 308 K.
Thus, dehydration, being an endothermic process, and crystal formation i.e. formation of (electrostatic) bonds, being an exothermic process,
both take place during the reactants-transition state step process
resulting in values of H and S smaller than those found for the
case where only dehydration occurs during the reactants-transition
state step process [precipitation, case (d)].
Reddy and Nancollas (1971), reporting on the kinetics of crystallization of calcium carbonate, state that the activation energy is relatively
high, 46.0 kJ mol1, and that the crystallization rate is independent of
the stirring speed. Wiechers et al. (1975, case (h)) suggest that the crystallization process conforms to the model for Ca2+ removal proposed by
Reddy and Nancollas (1971). The removal rate constant, k, is temperature dependent according to the Arrhenius relationship with Eact =
43.1 3.8 kJ mol 1. The high activation energy and other kinetic
parameters support the hypothesis that the crystallization process is
surface controlled.
Nancollas and Reddy (1971), in case (i) point out that the activation
energy for crystal growth of calcite is 46.0 4.2 kJ mol1,
thus supporting the proposed surface-controlled mechanism for
crystal growth. This value is considerably larger than the 17.6 kJ mol1
to be expected for a diffusion controlled reaction (Howard et al.,
1960), again pointing to the proposed interfacially controlled mechanism for calcium carbonate crystal growth. The assumptions made
of homogeneous nucleation and of simultaneous nucleation and
growth are, however, open to considerable criticism (Nancollas et al.,
1964). Data from Table 1 of the above work [case (i)] led us to
calculate H1 = 44.2 kJ mol 1, H2 = 26.5 kJ mol 1, S1 =
120.3 J K 1 mol 1, S2 = 181.92 J K 1 mol 1, G1 =
81.3 kJ mol1 at 308 K, G2 = 82.5 kJ mol1 at 308 K. The subscripts
1 and 2 refer to data that differ only according to mg seed crystal/
100 ml, the stirring rate (rpm) being the same.
A novel electrochemical system developed in case (j) (Hasson et al.,
2010) enables drastic reduction in the electrode area requirement by
directing the precipitation of calcium carbonate to occur in a seeds crystallization vessel rather than on the cathode. Kinetic coefcients reported in the literature are of two types: fundamental coefcients kRS based
on the actual crystallization area and coefcients kRM based on seeds
concentration. Literature values of the above kinetic coefcients kRS
and kRM are taken from Table 1 of case (j). The values of the two different kinetic coefcients result, as expected, in similar values of G
(85.1 vs. 88.86 kJ mol1 from kRS and kRM, respectively) but the values
of H and S are completely different implying completely different
149
Notes to Table 2:
(a) Experimental data in units of T in K and of k in: s1 (cases d, e, f, h, i,k, l, m, s), M1 s1 (cases g, k, p), m/s wt%2 (case j), l mm mol2 s1 (case n), mol/cm2 s (case o), mol m2 s1
(case q), l mol1 s1 (case r).
Case e*: for the supersaturation range between 2.5 and 11.
Case l*: activation energy for the nucleation of calcium sulfate dihydrate in 3 m NaCl solutions. The activation energy for case l was obtained using the induction time, tind.
(b) Calculated values.
(c) This work.
(d) Klepetsanis and Koutsoukos, 1991.
(e) Alimi et al., 2003.
(f) Merdhah and Yassin, 2008.
(g) Klepetsanis et al., 1999.
(h) Lancia et al., 1999.
(i) Prisciandaro et al., 2013.
(j) Jamialahmadi and Muller-Steinhagen, 2000.
(k) Liu and Nancollas, 1970.
(l) He et al., 1994.
(m) Prisciandaro et al., 2003.
(n) Liu and Nancollas, 1973.
(o) Smith and Sweett, 1971.
(p)1 and (p)2 Amjad and Masler, 1985.
(q) Yehia et al., 2011.
(r) Cetin et al., 2001.
(s) Liu and Nancollas, 1971.
150
2
energy is needed for the separation of the ions (Ca2+, CO2
3 , SO4 ) and
this has a value of ~ 20 kJ mol 1 increasing the 60 kJ mol1 value to
~80 kJ mol1 (as found). So the value of ~60 kJ mol1 is the free energy
of activation in the absence of foreign ions.
related. From Fig. 4 of case (o) we take data for comparison of the rates
of dissolution of normal (non-strained) calcite and calcite strained to a
dislocation density of 0.5 1091.0 109 cm2 as a function of pH at 3,
25 and 80 C. The data were taken for pH = 5.5. Our calculations prove
that the G values are similar (130.8 vs. 131.6 kJ mol1). The values
of G suggest retardation in comparison with the other cases of
Table 1 and this may be attributed to the increased ionic strength due to
KCl and HCl present in the solution. The very negative S suggests a
great degree of organization in the transition state compared to the reactants. The values of H are very low suggesting composite reactions.
Similar effect of the ionic strength, that is retardation, is observed in
cases: Table 1 case (f) and Table 2 case (q).
4.2. Processes involving CaSO4
4.2.1. Precipitation of CaSO4 in aqueous solutions
An understanding of the mechanism of CaSO4 formation in aqueous
solutions where precipitation takes place spontaneously due to high
supersaturation is of great importance for the control of undesirable
scale deposits. The time period that elapses between the attainment of
supersaturation and the appearance of the rst crystals is called the
induction time (He et al., 1994). An empirical relationship similar to
the Arrhenius equation (temperature dependence of the rate constant)
was suggested (Liu and Nancollas, 1975) for the effect of temperature
on induction period.
For the spontaneous precipitation of calcium sulfate dihydrate at
conditions of sustained supersaturation, an apparent activation energy
of 184 2 kJ mol1 [Table 2, case (d)] has been reported (Klepetsanis
and Koutsoukos, 1991). The kinetic analysis according to the Arrhenius
equation yielded a high activation energy value indicative, according to
the authors, of surface-controlled mechanisms. According also to the
authors, calcium sulfate dihydrate is formed in aqueous supersaturated
solutions by a polynuclear mechanism. Using the kinetic data of the
above work, we have calculated Eact, H, S and G [Table 2,
case (d)]. The H and the S values are positive suggesting a dissociative mechanism, i.e. going from the reactants to the transition state
the number of the various species increases. This may mean that
water molecules are released from the ionic environments of Ca2+(aq),
and SO42 (aq) in order to form the precipitate. G has the value
85.8 kJ mol1 at 308 K [Table 2 case (d)]. Due to the supersaturation
conditions the diffusion activation energy of ~20 kJ mol1 is obviously
not needed. This value of G is comparable with the value of
84.8 kJ mol 1 at 308 K for calcium carbonate precipitation [Table 1,
case (d)]. The high value of H suggests that a large amount of energy
is needed in order to break the bonds that exist between the ions and
the water molecules in the coordination sphere of the ions. Thus
dehydration of the ions is a main step in the reactants-transition
state process and is the main component of the H and the S
values. Hydration of the ions should result in H and S values.
Alimi et al. (2003) studying the kinetics of the precipitation of calcium sulfate dihydrate in a desalination unit, reported an activation energy value of 51.047 kJ mol1 [Table 2, case (e)]. Using data from the
above work we calculate Eact = 51.62 kJ mol1, H = 49 kJ mol1,
S = 117 J K1 mol1, G = 85.02 kJ mol1 at 308 K. The negative value of S suggests an associative mechanism, i.e. going from the
reactants to the transition state the number of the various species
decreases. This may suggest that the water molecules are released
from the ionic environments [Ca 2 +(aq) , and SO 4 2 (aq)] before the
slow rate-determining step. The combination of the positive and
negative ions leading to negative S i.e. to decrease of the number
of the various species [decrease of the degrees of freedom], is the
rate-determining step.
In a laboratory study and a prediction of calcium sulfate at highsalinity formation water (Merdhah et. al., 2008) the activation energy is
found to be 84.30 kJ mol1. Calculating H, S and G from the
data of this work [Table 2, case (f)], we nd that S is negative, as
151
(g), 84 kJ mol1 for case (h) and 89 kJ mol1 for case (i). This indicates
that, for the three cases (g), (h) and (i), similar mechanisms must be
taking place with the only difference being that for case (g) the diffusion
of the ions is needed which adds an amount of ~ 20 kJ mol1 to the
activation energy.
4.2.2. Crystallization of CaSO4 in aqueous solutions
Jamialahmadi and Muller-Steinhagen (2000, case (j)), reporting
on the crystallization of calcium sulfate dihydrate from phosphoric
acid, state that the effect of temperature on the growth rate constant
follows an Arrhenius relationship with an activation energy of
65.2 kJ mol1. From the Arrhenius plot of growth rate constant we get
data from which we calculate H = 37.4 kJ mol 1, S =
200.72 J K1 mol1 and G = 99 kJ mol1 at 308 K [Table 2, case
(j)]. The negative S value suggests an associative mechanism and
its large absolute value suggests a composite process (see previous
cases).
Liu and Nancollas (1970), studied the kinetics of crystal growth of
calcium sulfate dihydrate [case (k)] and reported an activation energy
value for the surface controlled crystal growth of 62.8 2 kJ mol1.
The authors declare that this value is appreciably larger than the
value 18.8 kJ mol 1 (Howard et al., 1960) to be expected on the
basis of pure mass transport control. Using data from the above work
we calculate Eact = 64.75 kJ mol 1, H = 62.24 kJ mol 1, S =
66.7 J K1 mol1, G = 82.78 kJ mol1 at 308 K.
The nucleation kinetics of calcium sulfate dihydrate in NaCl solutions
up to 6 m and 90 C was studied by He et al. (1994, case (l)). Using data
from the above work at 25, 50, 70, 90 C, NaCl 3.0 m, CaSO4 (aq)
180.0 mm and the corresponding induction times (in s), we calculated
G = 80.04 kJ mol1. Rate constants were calculated from induction
times.
Prisciandaro et al. (2003, case (m)) propose that citric acid has
a strong retarding effect towards gypsum nucleation. Several values
for the interfacial tension and activation energy have been estimated
as a function of citric acid concentration and of temperature. The
average of the activation energy values reported by the authors is
28.9 kJ mol 1. The values with the above average are comparable
with respect to that previously found in the absence of any additives
(Eact = 30 kJ mol 1 , Lancia et al., 1999). Thus we could say that
there is no actual retarding effect. On the other hand, our calculations reveal that G is 85.92 kJ mol 1 , H = 23.9 kJ mol 1 ,
S = 201.36 J K 1 mol 1 , implying an associative mechanism
and a composite reaction. The G value does not suggest strong
retardation.
Studying the linear crystallization and the induction-period of the
growth of calcium sulfate dihydrate crystals, Liu and Nancollas (1973)
reported that the linear crystallization of well-formed crystals of calcium sulfate dihydrate from supersaturated solutions needs the activation energy of 66.9 6.3 kJ mol 1 for the fast-growing faces. Using
data from this work we nd G = 85.12 kJ mol1 at 308 K.
Smith and Sweett (1971, case (o)), studying the crystallization of
calcium sulfate dihydrate (CaSO42H2O) reported that the value of the
rate constant indicated that the rate-controlling step was dehydration
of calcium ions. This suggests a positive value for S and a dissociative
mechanism. However, the value of S is found to be negative [Table 2,
case (o)] suggesting an associative process. The G value is 107.9 at
308 K implying that diffusion of the ions is taking place in the ratedetermining step.
Amjad and Masler (1985, case (p)) suggest that their results indicate
that the crystallization of CaSO42H2O in the presence of polyacrylates is
preceded by an induction period. Crystal growth of CaSO42H2O
proceeds with a rate close to that in pure supersaturated solution. The
authors report an activation energy of 64.9 kJ mol1 for the polymer
containing solution which is in excellent agreement, according to the
authors, with the Eact value reported for the CaSO42H2O seeded growth
in the presence of phosphonates (Liu et al., 1975). Our results show that
152
crystallization, case (j) for kRS coefcient] and by an associative mechanism, S b 0 [all the other cases, Tables 1 and 2]. The G values
are approximately the same whereas the values of H and S are
different.
The fact that the G values are almost the same for cases (d) of
Tables 1 and 2, suggests that the rate-determining step is the same
and this must be the dehydration of CaCO3 and CaSO4. The positive
values of S suggest dissociative mechanisms and actually this is the
mechanism when water molecules are released from the coordination
spheres of the cations [Ca2 +aq] and anions [CO32 (aq) and SO42 (aq)].
This dehydration process involves breaking of bonds and demands energy that is revealed as large values for H. In all the other cases,
S is negative implying an associative mechanism, i.e. increased
order in the transition state.
When a process takes place without the need for diffusion of the
ions, the free energy of activation is about 85 kJ mol 1 whereas
when there is a need for diffusion of the ions an additional amount
of ~ 20 kJ mol 1 is required. This amount is the activation energy
for the diffusion. Thus, in total, ~ 100 kJ mol 1 is needed for these
processes.
In the case of CaCO3, a very wide range is found for the values for H
(66.00162.00 kJ mol1) and S (501.00 to +248.00 J K1
mol1) while the G values cover a narrow range (7590 kJmol1).
An additional amount of +20 kJmol1 is needed when diffusion of the
ions takes place. Values of 120, 131 and 132 kJ mol1 are observed for
cases [case (f), cases (o), Table 1] where retardation is caused due to
the presence of foreign compounds.
Similarly, in the case of CaSO4, a very wide range is found for the
values for H (6.00122.00 kJ mol1) and S (342.00 to
+117.00 J K1 mol1), while a narrow range is found for the G
values (80.0089.00 kJ mol1). There is an additional amount of
+20 kJ mol1 for processes that include diffusion of the ions. A value
of 126 kJ mol1 is observed for one case [case (q), Table 2] where retardation is caused due to the presence of foreign compounds.
The Eact values vary between 63 and 164 kJ mol1 for CaCO3 and between 8 and 184 kJ mol1 for CaSO4, demonstrating once more that
the G value is a more realistic parameter, being almost the same for
similar processes.
The various small differences that appear in the values of G are
due to differences in ionic strength (the concentration and charge
of the foreign ions) that affect the rate constants and thus the activation parameters. The pH also has an effect, as does also the nature of the solvent.
The large absolute values of H and S reveal composite reactions. A composite reaction is, for example, one for which dehydration takes place (positive values of H and S ) followed by
association of the ions (negative values of H and S). The algebraic sum of the values is the total value of H and S.
Acceleration/retardation. The activation energy value of 46 kJ mol1 for
case (f) compared to the value of 155 kJ mol1 for case (d) does not
indicate retardation caused by EHDP, but, on the contrary, implies
acceleration of the reaction. However, the use of G instead of Eact
has been shown to be more realistic (Petrou, 2012), indicating here
the large retardation effect. G for case (f) is 120.2 kJ mol1 and for
case (d) is 84.8 kJ mol1. The larger value of G suggests a slower reaction. Also, in case (q), the values of Eact reported by the authors do not
justify retardation, but, on the contrary, suggest acceleration of the
reaction since small Eact values suggest large values of rate constants.
Again the use of G instead of Eact explains the retardation [20 vs.
126 kJ mol1, case (q)].
The addition of salt, for example NaCl, causes retardation of the crystallization process [case (q)]. The S value, ( 341.45 J K1 mol1)
suggests a very organized transition state. This is due to the attraction
and Ca2+, respectively.
of Na+ and Cl to SO2
4
Acknowledgments
Many thanks are due to all the authors that are included in the list of
references, who, with their valuable data, the high-level scientic work
both in experiments and in explanations, have given us signicant assistance in providing additional evidence concerning the activated steps
and the mechanisms for precipitation, crystallization and dissolution
of CaCO3 and CaSO4. We thank Pauline Zannia for her assistance. We
also thank the University of Athens for the nancial support of this
work.
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