Kinetics of the Heterogeneous Reaction of Calcium Bicarbonate Formation, with Special Reference to Copper Ion Inhibition.

Erga, Olav; Terjesen, S.G.; Cox, Robin A.; Peacocke, A. R.

doi:10.3891/acta.chem.scand.10-0872

Cited by 38 publications

(18 citation statements)

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“…As with the work of Svensson and Dreybrodt (1992), Erga and Terjesen's (1956) classic study of uninhibited calcite dissolution (that is, with EDTA, at four different pHs) can be turned, to validate the deductions made in this current paper. Firstly, Erga and Terjesen (1956) demonstrated that over the last *80 % of each of their runs the rate decreased linearly with the dissolved calcite concentration (The first 10 % or so was unavailable).…”

Section: Earlier Inhibition Work Offers Further Proof Of the So Modelmentioning

confidence: 56%

“…The inhibition of calcium carbonate dissolution by minor amounts of dissolved metal and other ions has been reported at pHs of about 4 (Erga and Terjesen 1956;Terjesen et al 1961;Nestaas and Terjesen 1969;Svensson and Dreybrodt 1992;Eisenlohr et al 1999;Vinson et al 2007) and 8.9 (Lea et al 2001). Since Erga and Terjesen (1956) reported that the addition of 4 9 10 -5 M EDTA overcame lM copper inhibition in the CaCO 3 -CO 2 -H 2 O system, the effect of EDTA was investigated here.…”

Section: The Effects Of Edta Upon Non-ideal Dissolutionmentioning

confidence: 93%

“…(Note that apparent is used here to avoid having to use effective, which is already in use for a different concept.) Success in both of these would have far-reaching consequences, such as facilitating the choice between two rival views of the chemical cause of non-ideal dissolution behaviour: one depending upon the poisoning of the surface (Erga and Terjesen 1956;Terjesen et al 1961;Nestaas and Terjesen 1969;Svensson and Dreybrodt 1992;Dreybrodt et al 1996;Eisenlohr et al 1999;Lea et al 2001;Vinson et al 2007;Morse et al 2007) as dissolution continues, the other upon a change in surface morphology as dissolution continues (Northwood and Lewis 1970;Busenberg and Plummer 1986;Compton et al 1986;Dove et al 2005;Morse et al 2007;Schott et al 2009;Xu et al 2012). The accumulated preliminary evidence for the exponential tails is persuasive.…”

Section: Equation For Calcite Dissolutionmentioning

confidence: 94%

“…Potentially then, the combination of the earlier findings (Svensson and Dreybrodt 1992;Dreybrodt et al 1996;Eisenlohr et al 1999) with those here points to the exponential tails being a ubiquitous property of the calcite used. Also, attempts to eradicate non-ideal dissolution behaviour in natural calcite by means of EDTA following Erga and Terjesen (1956) were only partially successful (Sect. 4.1.2).…”

Section: Evidence Of Exponential Tails From Existing Workmentioning

confidence: 99%

“…Since Erga and Terjesen (1956) reported that the addition of 4 9 10 -5 M EDTA overcame lM copper inhibition in the CaCO 3 -CO 2 -H 2 O system, the effect of EDTA was investigated here. Despite the earlier findings, the long tail to the concentration versus time plot did not disappear from a run conducted here at 22.0°C with 250-lm particles at pH 7.90, when EDTA at a concentration of 1.3 9 10 -3 M, that is, some 30 times that used by Erga and Terjesen (1956), was included. The plot split into two parts, one between 0 and 26 min and the other between 291 and 2930 min, with eight additional points occupying the transitional phase (35-162 min) between the two linear limbs.…”

Section: The Effects Of Edta Upon Non-ideal Dissolutionmentioning

confidence: 99%

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Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite

Truesdale

2015

Aquat Geochem

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Calcite batch dissolution kinetics behaviour has been described as complex for more than half a century. The dissolution of 100-to 250-lm particles of natural calcites at 20-35°C in Tris buffer or alkali at pHs 8-10.6 reveals that the non-ideal, long tails to the plot of calcium concentration versus time, are probably exponential. Equivalent alternative evidence from elsewhere for both calcite and gypsum is supplied. Inadequate kinetics templating of earlier results is believed to have obscured this exponential character, but rectification could induce a renaissance for batch dissolution study of calcite as well as for silicate and aluminosilicate minerals, too. The work extends a programme of study of the shrinking object (SO) model which has already considered a variety of substances such as sucrose, sodium chloride, gypsum, and silica gel, through which it has operationally defined ideal dissolution as an exponential rise in concentration with time, at high solids loadings. The SO model is limited to a constant surface area of the solid during dissolution. However, the possibility of explaining non-ideal dissolution of calcite by including a reduction in the apparent surface area during a dissolution, is explored here. In this the model shifts from an initial mode under one reaction rate constant to a terminal mode under a second rate constant, and by this the SO model is shown to share properties with a decelerating bolas-the South American hunting tool. The bolas model is consistent with earlier suggestions elsewhere that non-ideality arises from the surface being either poisoned or otherwise changed during dissolution. This current investigation derives from Empirical Kinetics, which is defined here as the wisdom of kinetics collected by the middle of the last half of the twentieth century. With the preliminary success gained with the exponential tails, the paper overcomes much confusion in the literature by differentiating direct measurements of rates of dissolution made for the purposes of chemical kinetics, from those needed for biogeochemical field purposes.

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Section: Earlier Inhibition Work Offers Further Proof Of the So Modelmentioning

confidence: 56%

Section: The Effects Of Edta Upon Non-ideal Dissolutionmentioning

confidence: 93%

Section: Equation For Calcite Dissolutionmentioning

confidence: 94%

Section: Evidence Of Exponential Tails From Existing Workmentioning

confidence: 99%

Section: The Effects Of Edta Upon Non-ideal Dissolutionmentioning

confidence: 99%

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Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite

Truesdale

2015

Aquat Geochem

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Kinetics of Dissolution of Limestone Slurries in Sulfuric Acid

Dı́az

Fonseca

Coca

1985

Chemie Ingenieur Technik

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Limestone slurries are extensively used for neutralization of mining and chemical process effluents and for scrubbing of SOz from stack gases, because of the availability and low cost of limestone. There are, however, several drawbacks to the use of limestone in neutralizing and scrubbing processes, notably its low solubility and sluggish reactivity, as well as the disposal of large amounts of sludge produced. Factors such as the type of rock, particle size, pH, temperature, and effluent composition affect the solubility and reactivity of the limestone particles. Kinetic studies on the rate of dissolution usually assume that mass transfer with chemical reaction takes place in the diffusional regime, as the reactions involved are fast [l-51. In this work, data are reported for the rate of dissolution of limestone in sulfuric acid at pH = 7 as a function of particle size, temperature, and presence of common ions. A simple model for the dissolution process is proposed which allows a good fit of the experimental data and evaluation of the mass transfer coefficients. ExperimentalLimestone dissolution in sulfuric acid was studied in a pyrex glass jacketed stirred tank. The impeller was of the vaned disc type with a diameter of 2 D/5 ( D = 10 cm, tank diameter) which had 6 blades with a height of D/IO. Four baffles with a width of D/8 were inserted. The limestone was supplied by Tudela Veguin (Oviedo, Spain); its purity was of the order of 98% in CaC03 and contained 0.2% S O z . Samples were sieved for 15 min and fractions of 325-400, 170-200, 60-70, 35-40, and 16-18 mesh were collected. From the size distribution data (a Sartorius 4600 sedimentation balance was used for particles smaller than 170 mesh) average surface areas of 4000; 2100; 245; 180, and 80 cm2/g respectively were obtained. The former fractions were also collected after 2 h sieving, and some samples t , s Fig. 1. limestone (25"C, 15 min sieving, 640 min-').Effect of the particle diameter on the rate of dissolution of * M . Diaz, L. Fonseca, and Prof. J. Coca (to whom correspondence should be addressed), Department of Chemical Engineering, University of Oviedo, 33007 Oviedo, Spain.were washed with hexane after sieving in order to remove fines stuck to the particles. Every experiment was started by placing 800 cm3 of distilled water in the tank and adjusting its p H to 7 by addition of NaOH. Once a constant temperature was reached, 8 g of limestone of a certain particle size was added to the tank, except in the case of the two smallest sizes, where 2 g was added. The rate of limestone dissolution was measured by constantly maintaining the pH value of 7 by adding 0.05N H2S04 and recording the amount added as a function of time. The tank was sealed in each experimental run and nitrogen was passed through the space above the reacting mixture at a rate of 40 Vh (in some experiments air was passed instead of nitrogen for comparison) Effect of the temperature on the rate of dissolution of lime- ResultsThe effect of particle size on the rate of dissolution is sh...

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Effect of limestone type and grind on SO₂ scrubber performance. The cost‐reduction effect of finer limestone grinding on SO₂ scrubber efficiency can be very considerable

et al. 1982

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Kinetics of the Heterogeneous Reaction of Calcium Bicarbonate Formation, with Special Reference to Copper Ion Inhibition.

Cited by 38 publications

References 0 publications

Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite

Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite

Kinetics of Dissolution of Limestone Slurries in Sulfuric Acid

Effect of limestone type and grind on SO₂ scrubber performance. The cost‐reduction effect of finer limestone grinding on SO₂ scrubber efficiency can be very considerable

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Kinetics of the Heterogeneous Reaction of Calcium Bicarbonate Formation, with Special Reference to Copper Ion Inhibition.

Cited by 38 publications

References 0 publications

Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite

Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite

Kinetics of Dissolution of Limestone Slurries in Sulfuric Acid

Effect of limestone type and grind on SO2 scrubber performance. The cost‐reduction effect of finer limestone grinding on SO2 scrubber efficiency can be very considerable

Contact Info

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Effect of limestone type and grind on SO₂ scrubber performance. The cost‐reduction effect of finer limestone grinding on SO₂ scrubber efficiency can be very considerable