• Title/Summary/Keyword: Acid dissociation constant $(pK_a)$

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Nonlinear pH Control Using a Three Parameter Model

  • Lee, Jie-Tae;Park, Ho-Cheol
    • Transactions on Control, Automation and Systems Engineering
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    • v.2 no.2
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    • pp.130-135
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    • 2000
  • A two parameter model of a single fictitious weak acid with unknown dissociation constant has been successfully applied to design a neutralization system for many multi-component acid streams. But there are some processes for which above two parameter model is not satisfactory due to poor approxmation of the nonlinearity of pH process. Here, for etter control of wide class of multi-component acid streams, a three parameter model of a strong acid and a weak acid with unknown dissociation constant is proposed. The model approximates effectively three types of largest gain variation nonlinearities. Based on this model a nonlinear pH control system is designed. Parameters can eeasily estimated since their combinations appear linearly in the model equations and nonlinear adaptive control system may also be constructed just as with the two parameter model.

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Determination of Dissociation Constant of Hydrogen Cupferrate in Methanol-Water and 2-Propanol-Water Solution (Methanol-물 및 2-Propanol-물의 混合溶媒에서의 Hydrogen Cupferrate의 酸解離常數의 決定)

  • Si-Joong Kim;Chang-Ju Yoon;In-Soon Chang
    • Journal of the Korean Chemical Society
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    • v.10 no.3
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    • pp.119-128
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    • 1966
  • The glass electrode was empirically calibrated in methanol-and 2-propanol-water mixed solvents, by means of which the pH-meter reading could be converted to stoichiometric hydrogen ion concentration. The thermodynamic dissociation constants of hydrogen cupferrate in methanol-and 2-propanol-water solution were potentiometrically determined with the changes in composition of organic solvents at 0.01 and 0.05 of the ionic strength and 25$^{\circ}C$. The empirical formula of the constants with mole fraction (n) of the organic solvent are as follow: methanol-water solution $pK_a$= 2.24n + 4.29 at ${\mu}$ = 0.01 n = 0.0476∼0.642 $pK_a$ = 2.35n + 4.38 at ${\mu}$ = 0.05 n= 0.0446~0.642 2-propanol-water solution $pK_a$= 5.50n + 4.48 at ${\mu}$ = 0.05 n = 0.0253~0.259 The relationships between $pK_a$ of acetic acid, propionic acid and HCup and dielectric constant of some mixed solvents were discussed. It would be considered that the factors effecting $pK_a$ value of weak acid in mixed-solvent are not only dielectric constants but acid-base character and solvation effect of the solvent, etc.

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Study of Protonation Behaviour and Distribution Ratios of Hydroxamic Acids in Hydrochloric and Perchloric Acid Solutions Through Hammett Acidity Function, Bunnett-Olsen and Excess Acidity Method

  • Agarwal, Manisha;Singh, Priyanka;Pande, Rama
    • Korean Chemical Engineering Research
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    • v.57 no.2
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    • pp.164-171
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    • 2019
  • The protonation parameters, dissociation constants ($pK_{BH^+}$) of conjugate acid, slope values (m, ${\phi}$ and $m^*$) and correlation coefficients (r) of hydroxamic acids were determined by Hammett acidity function method, Bunnett-Olsen method and excess acidity method in hydrochloric and perchloric acid solutions. Effect of acid concentration on partition and percentage protonation was also studied. $pK_{BH^+}$ values show that hydroxamic acids do not behave as Hammett bases, but hydroxamic acids behave as weak bases in strong acidic solutions. The values of $pK_{BH^+}$ obtained through Bunnett-Olsen method and excess acidity method were compared with the Hammett acidity function. ChemAxon's MarvinSketch 6.1.5 software was also used for determining $pK_a$, pI and microspecies distribution (%) of hydroxamic acids with pH. Hydrogen donor and acceptor values and logD were also obtained. The results show that N-p-chlorophenyl-4-bromobenzohydroxamic acid has the highest $pK_a$ and lowest logD values. On the contrary, N-phenyl-3,5-dinitrobenzohydroxamic acid has lowest the $pK_a$ and highest logD values.

Environmentally Assisted Cracking of Alloys at Temperatures near and above the Critical Temperature of Water

  • Watanabe, Yutaka
    • Corrosion Science and Technology
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    • v.7 no.4
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    • pp.237-242
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    • 2008
  • Physical properties of water, such as dielectric constant and ionic product, significantly vary with the density of water. In the supercritical conditions, since density of water widely varies with pressure, pressure has a strong influence on physical properties of water. Dielectric constant represents a character of water as a solvent, which determines solubility of an inorganic compound including metal oxides. Dissociation equilibrium of an acid is also strongly dependent on water density. Dissociation constant of acid rises with increased density of water, resulting in drop of pH. Density of water and the density-related physical properties of water, therefore, are the major governing factors of corrosion and environmentally assisted cracking of metals in supercritical aqueous solutions. This paper discusses importance of "physical properties of water" in understanding corrosion and cracking behavior of alloys in supercritical water environments, based on experimental data and estimated solubility of metal oxides. It has been pointed out that the water density can have significant effects on stress corrosion cracking (SCC) susceptibility of metals in supercritical water, when dissolution of metal plays the key role in the cracking phenomena.

A Study on the Measurement of Dissociation Constant of Organic Acid with FIA (FIA에 의한 유기산의 해리상수 측정에 관한 연구)

  • Rhee, Jae-Seong;Park, Hyun-Mee;Kim, Hee-Jin;Lee, Kang-Bong;Dasgupta, Purnendu K.
    • Analytical Science and Technology
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    • v.7 no.2
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    • pp.173-179
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    • 1994
  • The point of present study was focused on developing the method for the determination of dissociation constant by means of FIA conjunction with Diode Array Spectrphotometry or spectrophotometry along with small amount of Bromocresol Green(mg order) within short time. On the calculation with computer, the indicator with pK=7 has been shown the most sensitive reaction when little amount of base or acid has been added. The pKa of Bromothymol Blue and Bromocresol Green were measured as 7.31 and 4.82 respectively with spectrophotometry after activity correction by Kielland method (Reported value by Bishop, 7.30 and 4.79). The pKa of Bromocresol Green by FIA was obtained as 4.78 and was comparable with other values determined by other methods.

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THE RELATIONSHIP BETWEEN BUFFER INDEX CURVE AND FERMENTATION QUALITY OF SILAGE

  • Kim, K.H;Uchida, S.
    • Asian-Australasian Journal of Animal Sciences
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    • v.4 no.1
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    • pp.67-71
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    • 1991
  • The purpose of this study was to investigate the possibility of using the buffer index curve as a criterion of silage quality evaluation. The buffer index (or buffer capacity, $\beta$) value is the amount of 0.1N NaOH consumed in titrating from the beginning to the end of the chosen pH step. This value equals the slope of the titration curve at the chosen pH range (${\beta}={\Delta}NaOH/{\Delta}pH$). There were two patterns of buffer index curve. Poorly preserved silages had a peak at pH 5.0, whereas with well preserved silages the peaks tended to rise to the pH 3.75 or 4.00. Well preserved, wilted silages with high pH also appeared to have peak values at pH 3.75 or 4.00. There was a high positive correlationship between the concentration of lactic acid and peak value of good quality silage (r = 0.994, p < 0.01). Also a high positive correlationship (r = 0.899, p < 0.001) was found between the sums of concentration of acetic and butyric acids and the peak values of poor quality silages. The results of these experiments verified the value of the buffer index method as a criterion of silage quality evaluation.

Studies on the Dissociation Constant of Benzoic Acid and Substituted Benzoic Acids in Methanol-Water Mixtures by Conductometric Method (메탄올-물 혼합용매에서 전도도법에 의한 벤조산 및 치환된 벤조산의 해리에 관한 연구)

  • Min Soo Cho;Hyoung Ryun Park;Soon Ki Rhee;Kye Soo Lee;Bon Su Lee
    • Journal of the Korean Chemical Society
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    • v.35 no.3
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    • pp.196-203
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    • 1991
  • The $pK_a$ values of benzoic acid and meta, para-halogen substituted benzoic acids in MeOH-$H_2O$ mixtures (0∼80% of MeOH) have been determined at 25$^{\circ}$C using a conductometric method on the basis of the Fuoss-Kraus equation, and further verified using modified conductometric method of Gelb. The dependence of $pK_a$ on halogen substituents has been discussed in terms of substituent-constant (${\sigma}$), which is devided into electron-withdrawing inductive contribution (${\sigma}_1$) and electron-donating ${\pi}$-resonance one (${\sigma}_R$). The linear-dependence of ${\sigma}_1$'s on $D^{-1}$ with positive slope and that of ${\sigma}_R$'s on $D^{-1}$ with negative slope have been interpreted on the basis of field effect and through-space interaction of ${\pi}$-lone pair of halogen substituent and ionization center via ${\pi}$-system of benzene ring.

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Characterization of High Affinity Juvenile Hormone Binding protein in the Hemolvmph of Bombyx mori L. (누에나방 혈림프의 high affinity 유약호르몬 결합단백질의 특성)

  • 박철호;김학열
    • The Korean Journal of Zoology
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    • v.37 no.4
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    • pp.495-503
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    • 1994
  • Hemolymph SHBP (hJHBP) was partially purified from last instar larvae of Bombyx zori by gel filtration and their optimal reaction conditions of dextrin coated charcoal binding assay were determined. Dissociation constant (KD) of hJHBP for JH III was calculated to be 1.45 $\times$ 10-7 M at $4^{\circ}C.$ The molecular weight of hJHBP was estimated to be 30 kDa by gel filtration on a calibrated Sephadex G-100 column and 33 kDa by SDS-PAGE. These results indicate that hSHBP consists of a single polvpeptide chain. Isoelectric point of hJHBP was found to be pH 5.1 and 19 of the first 20 amino acid residues were determined from N-terminus of purified hJHBP.

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Interaction of ${\alpha}$-Ketoglutarate Dehydrogenase Complex with Allosteric Regulators Detected by a Fluorescence Probe, 1,1'-bi(4-aniline)naphthalene-5,5'-disulfonic acid, an Inhibitor of Catalytic Activity

  • Hong, Sung-Youl;Bak, Choong-Il;Ryu, Jae-Ha;Song, Byoung-J.;Huh, Jae-Wook
    • BMB Reports
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    • v.29 no.3
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    • pp.230-235
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    • 1996
  • The interaction of ${\alpha}-ketoglutarate$ dehydrogenase complex (${\alpha}-KGDC$) with a hydrophobic fluorescent probe [1,1'-bi(4-aniline)naphthalene-5,5'-disulfonic acid] (bis-ANS) was studied. The punfied ${\alpha}-KGDC$ was potently inhibited by bis-ANS with an apparent half maximal inhibitory concentration ($IC_{50}$) of 9.8 ${\mu}m$ at pH 8.0. The catalytic activities of both the E1o and E2o subunits were predominantly inhibited while that of the E3 component was hardly affected. The binding of bis-ANS to the enzyme caused a marked enhancement and blue shift from 523 nm to 482 nm in the fluorescence emission spectrum. The dissociation constant ($K_d$) and the number of binding sites (n) were calculated to be 0.87 mM and 158, respectively. Allosteric regulators such as purine nucleotides and divalent cations further increased the fluorescence intensity of the $bis-ANS-{\alpha}-KGDC$ binary complex. These data suggest that the binding of these allosteric regulators to ${\alpha}-KGDC$ may cause the conformational changes in the enzyme and that bis-ANS could be used as a valuable probe to study the interaction of the multi-enzyme complex and its allosteric regulators.

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