The Kinetics of Dissolution of II–VI Semiconductor Compounds in Nonoxidizing Acids

Locker, L. D.; DeBruyn, P.L

doi:10.1149/1.2411654

Cited by 26 publications

(17 citation statements)

References 2 publications

(2 reference statements)

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“…In other words, the rate of the reverse reaction for CaCO 3 is given by eq 30.Equation 30 corresponds exactly with the kinetics of the reverse reaction reported by Sjöberg. 20 A similar expression was reported by Locker and deBruyn 18 for ZnS and CdS and confirmed by Crundwell and Verbaan 19 for ZnS from a variety of different origins. Therefore, the generality of eq 26 is established because it successfully applies to a variety of dissolution systems.…”

Section: Characteristic Behavior Between Rate Control and Equilibriumsupporting

confidence: 84%

“…As mentioned in Introduction, the experimental results for NaCl, ZnS, and CaCO 3 all display the same half-order kinetics for the reverse reaction. 18−20 The experimental method for evaluating the reverse reaction is to measure the equilibrium condition, as explained by Crundwell and Verbaan. 19 Under these conditions, the concentrations of the products are high, and eq 26 readily reproduces the half-order kinetics seen experimentally.…”

Section: Characteristic Behavior Between Rate Control and Equilibriummentioning

confidence: 99%

“…The reverse reactions for ZnS, CdS, and CaCO 3 all show analogous kinetic laws for the reverse reactions. 18−20 Specifically, their orders of reaction for the reverse reaction (precipitation) are one-half in a manner analogous to eq 8.…”

Section: Introductionmentioning

confidence: 99%

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Path from Reaction Control to Equilibrium Constraint for Dissolution Reactions

Crundwell

2017

ACS Omega

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Although dissolution reactions are widespread and commonplace, our understanding of the factors affecting the rate of dissolution is incomplete and consequently the kinetics of these reactions appear complicated. The focus in this work is on the behavior of the rate as conditions approach equilibrium. The reverse reaction is often treated in terms of chemical affinity, or saturation state. However, the implementation of the chemical affinity model fails, requiring arbitrary empirical adjustments. In this study, a mechanism of dissolution is proposed that describes both the fractional orders of reaction with respect to H + and OH – and correctly describes the approach to equilibrium. The mechanism is based on the separate removal of anions and cations from the surface, which are coupled to one another through their contribution to and dependence on the potential difference across the interface. Charge on the surface, and hence potential difference across the interface, is caused by an excess of ions of one sign and is maintained at this stationary state by the rate of removal of cations and anions from the surface. The proposed model is tested using data for NaCl (halite), CaCO 3 (calcite), ZnS (sphalerite), NaAlSi 3 O 8 (albite), and KAlSi 3 O 8 (K-feldspar). An important feature of the proposed model is the possibility of “partial equilibrium”, which explains the difficulties in describing the approach to equilibrium of some minerals. This concept may also explain the difficulties experienced in matching rates of chemical weathering measured in laboratory and field situations.

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Section: Characteristic Behavior Between Rate Control and Equilibriumsupporting

confidence: 84%

Section: Characteristic Behavior Between Rate Control and Equilibriummentioning

confidence: 99%

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Path from Reaction Control to Equilibrium Constraint for Dissolution Reactions

Crundwell

2017

ACS Omega

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“…Pulse2™4 and 7 radiolysis5™8 studies have shown that the sulfhydryl-containing amino acid cysteine (HSCH2CH-(NH3+)COOH)9 is highly reactive toward eaq-, • , and • radicals. Also product yields from 10-3 and -2 M solutions in the pH range 0-8 can be satisfactorily explained by the following reactions: eaq-+ RSH -» R-+ HS" (f=^H2s) (1) eaq-+ H+ -* H- •H + RSH --SH + RH (6) •SH + RSH -H2S + RS- (7) •OH + RSH -H20 + RS• (8) RS-+ RS--* RSSR (9) RSH ^RS-+ H+ (10) RS. + RS-^RSS-R (11) RS-+ RSS-R -» RS" + RSSR (12) The abbreviated formula RSH (R = CH2CH(NH3+)COOH) is used here, since the observed chemical changes involve only the sulfhydryl group.…”

Section: Introductionmentioning

confidence: 82%

.gamma. Radiolysis of penicillamine in deaerated 1 M perchloric acid

Goyal¹

1976

J. Phys. Chem.

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The products of radiolysis of penicillamine in 1 M HCIO4 are reported and their yields discussed. The reactions of • and -CH2OH are qualitatively similar to those observed for cysteine and produce primarily RS• radicals. However, the secondary reactions of RS• radicals give rise to a substantially higher yield of trisulfide (RSSSR) than is observed with cysteine. This appears to be due to the presence of weaker C-S bonds in the tertiary C-SH compound and to the fact that this bond can be broken as a result of interactions between RS• and RSH, possibly via the formation of a RSS(H)R intermediate. The magnitude of the rate constant ratio fe3(fc4 + ke)-1 at 1 ± 1 °C is 0.54 ± 0.10. At 23 6C it was found to be 0.50 ± 0.10 in good agreement with an earlier value of O.44.11

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“…Both Locker and de Bruyn [62] and Crundwell and Verbaan [68] reported that the orders of the reverse reaction had values of 0.5 with respect to both Zn 2+ and H 2 S (see Table 4). To describe these results, select a value of 2 for t and consider only terms for the reverse reactions in Equation ( 16).…”

Section: Testing the Surface-vacancy Model-reverse Reaction 81 Orders Of Reaction For The Reverse Reactionmentioning

confidence: 99%

The Surface-Vacancy Model—A General Theory of the Dissolution of Minerals and Salts

Crundwell

2021

Minerals

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The kinetics of the dissolution of salts and minerals remains a field of active research because these reactions are important to many fields, such as geochemistry, extractive metallurgy, corrosion, biomaterials, dentistry, and dietary uptake. A novel model, referred to as the surface-vacancy model, has been proposed by the author as a general mechanism for the primary events in dissolution. This paper expands on the underlying physical model while serving as an update on current progress with the application of the model. This underlying physical model envisages that cations and anions depart separately from the surface leaving a surface vacancy of charge opposite to that of the departing ion on the surface. This results in an excess surface charge, which in turn affects the rate of departing ions. Thus, a feedback mechanism is established in which the departing of ions creates excess surface charge, and this net surface charge, in turn, affects the rate of departure. This model accounts for the orders of reaction, the equilibrium conditions, the acceleration or deceleration of rate in the initial phase and the surface charge. The surface-vacancy model can also account for the effect of impurities in the solution, while it predicts phenomena, such as ‘partial equilibrium’, that are not contemplated by other models. The underlying physical model can be independently verified, for example, by measurements of the surface charge. This underlying physical model has implications for fields beyond dissolution studies.

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The Kinetics of Dissolution of II–VI Semiconductor Compounds in Nonoxidizing Acids

Abstract: ANODIC FILMS ON ZINC 1659 microprobe x-ray analyzer, while David Fisher and John Bartlett did the atomic absorption analysis. The identification of the anodic films by x-ray and electron diffraction was the work of William Dorfeld and Louis Osika.

Cited by 26 publications

References 2 publications

Path from Reaction Control to Equilibrium Constraint for Dissolution Reactions

Path from Reaction Control to Equilibrium Constraint for Dissolution Reactions

.gamma. Radiolysis of penicillamine in deaerated 1 M perchloric acid

The Surface-Vacancy Model—A General Theory of the Dissolution of Minerals and Salts

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