Cyanide Thermodynamics. III. Enthalpies and Entropies of Ionization of Water and Hydrogen Cyanide

1996 ◽  
Vol 49 (6) ◽  
pp. 651 ◽  
Author(s):  
JS Solis ◽  
PM May ◽  
G Hefter
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Stability Constant ◽  
Hydrogen Cyanide ◽  
Infinite Dilution ◽  
Medium Effect ◽  
Titration Calorimetry ◽  
Enthalpy Changes ◽  
The Difference ◽  
Ionization Of Water

The heats (enthalpy changes) associated with the ionization of water and of hydrogen cyanide have been determined by titration calorimetry at 25�C as a function of ionic strength up to 5 M in both NaCl and NaClO4 media. The enthalpy changes for both reactions exhibit a 'medium effect' with ?H being more positive in NaCl than in NaClO4 and with the difference becoming more pronounced with increasing ionic strength. This is attributed to the greater solvation of Cl- cf. CN- in aqueous solution. The present ?H values are similar to previous published results at high ionic strengths, and are in excellent agreement with the well established literature values at infinite dilution. The present ?H values were combined with literature stability constant data to calculate the corresponding entropies for the ionization of H2O and HCN as a function of ionic strength.

scholarly journals Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2+

Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7087
Author(s):  
Clemente Bretti ◽  
Roberto Di Pietro ◽  
Paola Cardiano ◽  
Olivia Gomez-Laserna ◽  
Anna Irto ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Infinite Dilution ◽  
Natural Waters ◽  
Supporting Electrolyte ◽  
Formation Constants ◽  
Medium Effect ◽  
Diacetic Acid ◽  
Complex Species ◽  
Enthalpy Changes ◽  
Negative Effect

The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2−, CdHL−, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3−, whose formation constant values at infinite dilution were log β = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCd ≥ CGLDA and concentrations of >0.1 mmol dm−3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration.

Inerte Amminkomplexe als mehrwertige Kationsäuren in wäßriger Lösung / Inert Ammine Complexes as Multivalent Cationic Acids in Aqueous Solution

1980 ◽  
Vol 35 (9) ◽  
pp. 1096-1103 ◽  
Author(s):  
Matthias Kretschmer ◽  
Lutwin Labouvie ◽  
Karl-W. Quirin ◽  
Helmut Wiehn ◽  
Ludwig Heck
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Spectrophotometric Method ◽  
Complex Cation ◽  
Aqua Ligand ◽  
Second Step ◽  
Acidity Constants ◽  
Ammine Complexes ◽  
Temperature Variations ◽  
Enthalpy Changes

Acidity constants of ammine complexes of tetravalent platinum in aqueous solutions have been determined by a spectrophotometric method at very low ionic strengths and extrapolated to zero ionic strength. Temperature variations of pK-values (25 °C and 50 °C) yield thermodynamic parameters for two successive deprotonation steps of hexaammineplatinum(IV), pentaamminechloroplatinum(IV), and tris(ethylenediamine)pla- tinum(IV) complexes and for the deprotonation of pentaammineaquacobalt(III) ion.The enthalpy changes for the first and second steps are similar and range from 50 to 75 kJ/mole while for the aqua ligand of Co(III) 33 kJ/mole are found. The very large dif­ference in the entropy changes (about 70 to 80 J/K mole for the first step and -10 to + 20 J/K mole for the second step) is interpreted by a model of solvation change. The primary hydration sphere of strongly oriented and immobilized water dipoles around the highly charged complex cation is transformed to a hydrogen-bonded solvation sheath when the electric field of the complex is weakened upon release of the first proton.

scholarly journals Understanding the Solution Behavior of Epinephrine in the Presence of Toxic Cations: A Thermodynamic Investigation in Different Experimental Conditions

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 511 ◽  
Author(s):  
Francesco Crea ◽  
Concetta De Stefano ◽  
Anna Irto ◽  
Gabriele Lando ◽  
Stefano Materazzi ◽  
...  
Keyword(s):  
Ionic Strength ◽  
Complex Formation ◽  
Formation Constants ◽  
Titration Calorimetry ◽  
Interaction Theory ◽  
Thermodynamic Investigation ◽  
Experimental Conditions ◽  
Complex Formation Constants ◽  
Specific Ion Interaction Theory ◽  
Enthalpy Changes

The interactions of epinephrine ((R)-(−)-3,4-dihydroxy-α-(methylaminomethyl)benzyl alcohol; Eph−) with different toxic cations (methylmercury(II): CH3Hg+; dimethyltin(IV): (CH3)2Sn2+; dioxouranium(VI): UO22+) were studied in NaClaq at different ionic strengths and at T = 298.15 K (T = 310.15 K for (CH3)2Sn2+). The enthalpy changes for the protonation of epinephrine and its complex formation with UO22+ were also determined using isoperibolic titration calorimetry: ΔHHL = −39 ± 1 kJ mol−1, ΔHH2L = −67 ± 1 kJ mol−1 (overall reaction), ΔHML = −26 ± 4 kJ mol−1, and ΔHM2L2(OH)2 = 39 ± 2 kJ mol−1. The results were that UO22+ complexation by Eph− was an entropy-driven process. The dependence on the ionic strength of protonation and the complex formation constants was modeled using the extended Debye–Hückel, specific ion interaction theory (SIT), and Pitzer approaches. The sequestering ability of adrenaline toward the investigated cations was evaluated using the calculation of pL0.5 parameters. The sequestering ability trend resulted in the following: UO22+ >> (CH3)2Sn2+ > CH3Hg+. For example, at I = 0.15 mol dm−3 and pH = 7.4 (pH = 9.5 for CH3Hg+), pL0.5 = 7.68, 5.64, and 2.40 for UO22+, (CH3)2Sn2+, and CH3Hg+, respectively. Here, the pH is with respect to ionic strength in terms of sequestration.

scholarly journals Activity corrections for ionic equilibria in aqueous solutions

1980 ◽  
Vol 58 (12) ◽  
pp. 1253-1257 ◽  
Author(s):  
Mian S. Sun ◽  
Donald K. Harriss ◽  
Vincent R. Magnuson
Keyword(s):  
Ionic Strength ◽  
Stability Constant ◽  
Aqueous Solutions ◽  
General Formula ◽  
Stability Constants ◽  
Ionic Equilibria ◽  
Ion Activity ◽  
The Difference ◽  
Single Ion Activity ◽  
The Stability

Activity corrections for ionic equilibria in aqueous solutions at 25 °C and ionic strengths up to 0.5 have been investigated. An empirical formula for activity corrections was generated by statistically fitting stability constant data for approximately 540 complexes, for which both thermodynamic and concentration stability constants were known, to a modified Debye – Hückel relationship. The general formula is[Formula: see text]χ > 0, where Δ log K is the difference in the logarithms of the stability constants at infinite dilution and finite I (I ≤ 0.5), and χ is an even integer dependent only on the stoichiometry and charge of the ions involved. Activity correction formulae for ionic equilibria involving classes of ligands (amino acid, inorganic, amine, and organic acid) also were developed. The general formula predicts stability constant corrections within 0.1 log unit for 87 % of the data used at ionic strength 0.1 and 64 % of the data at ionic strength 0.5. In addition, single ion activity coefficients as a function of ionic strength, 0 < I ≤ 0.5, are presented.

Intrinsic acidities of carbon acids: the nitroalkanes. Solvation effects in water and DMSO

1977 ◽  
Vol 55 (19) ◽  
pp. 3474-3479 ◽  
Author(s):  
J. B. Cumming ◽  
T. F. Magnera ◽  
P. Kebarle
Keyword(s):  
Aqueous Solution ◽  
High Pressure ◽  
Gas Phase ◽  
Methyl Substitution ◽  
Charge Localization ◽  
Enthalpy Changes ◽  
Gas Phase Acidity ◽  
Protic Solvents ◽  
Carbon Acids ◽  
The Difference

The ion equilibria R1H + R2− = R1− + R2H involving nitroalkanes and compounds with known gas phase acidity were measured at 500 K with a pulsed high pressure mass spectrometer. The resulting ΔG0°= −RT ln K combined with calculated ΔS0 values lead to the corresponding ΔH changes. The enthalpy changes are used for the evaluation of the difference between the bond dissociation energy and the electron affinity D(R—H) – EA(R). The values obtained are: CH3NO2 44.0, CH3CH2NO2 43.7, (CH3)2CHNO2 43.0 kcal/mol. D(R—H) – EA(R) is a measure of the gas phase acidity. The nearly equal gas phase acidities of the nitroalkanes above are due to a decrease of D(R—H) and to a decrease of EA(R) with methyl substitution. In aqueous solution the acidities are known to increase substantially for the above nitroalkane order. Decrease of EA with methyl substitution indicates that there will be more charge localization on the O atoms in R− with methyl substitution. This leads to better H bonding and solvation of R− in protic solvents. This explains the higher acidity of the methyl substituted nitroalkanes in aqueous solution. The acidities in DMSO are closer to those in the gas phase since DMSO is not so sensitive to the charge distribution in R−.

scholarly journals Effect of calcium ions on the irreversible denaturation of a recombinant Bacillus halmapalus alpha-amylase: a calorimetric investigation

2003 ◽  
Vol 373 (2) ◽  
pp. 337-343 ◽  
Author(s):  
Anders D. NIELSEN ◽  
Claus C. FUGLSANG ◽  
Peter WESTH
Keyword(s):  
Calcium Ions ◽  
Calcium Binding ◽  
Thermal Inactivation ◽  
Binding Constants ◽  
Ion Concentration ◽  
Effect Of Temperature ◽  
Titration Calorimetry ◽  
Free Calcium ◽  
Enthalpy Changes ◽  
The Difference

The effect of temperature and calcium ions on the denaturation of a recombinant α-amylase from Bacillus halmapalus α-amylase (BHA) has been studied using calorimetry. It was found that thermal inactivation of BHA is irreversible and that calcium ions have a significant effect on stability. Thus an apparent denaturation temperature (Td) of 83 °C in the presence of excess calcium ions was observed, whereas Td decreased to 48 °C when calcium was removed. The difference in thermal stability with and without calcium ions has been used to develop an isothermal titration calorimetric (ITC) procedure that allows simultaneous determination of kinetic parameters and enthalpy changes of the denaturation of calcium-depleted BHA. An activation energy EA of 101 kJ/mol was found for the denaturation of calcium-depleted BHA. The results support a kinetic denaturation mechanism where the calcium-depleted amylase denatures irreversibly at low temperature and if calcium ions are in excess, the amylase denatures irreversibly at high temperatures. The two denaturation reactions are coupled with the calcium-binding equilibrium between calcium-bound and -depleted amylase. A combination of the kinetic denaturation results and calcium-binding constants, determined by isothermal titration calorimetry, has been used to estimate kinetic stability, expressed in terms of the half-life of BHA as a function of temperature and free-calcium-ion concentration. Thus it is estimated that the apparent EA can be increased to approx. 123 kJ/mol by increasing the free-calcium concentration.

scholarly journals Transdiagnostic comparison of visual working memory capacity in bipolar disorder and schizophrenia

2021 ◽  
Vol 9 (1) ◽  
Author(s):  
Catherine V. Barnes-Scheufler ◽  
Caroline Passow ◽  
Lara Rösler ◽  
Jutta S. Mayer ◽  
Viola Oertel ◽  
...  
Keyword(s):  
Bipolar Disorder ◽  
Working Memory ◽  
Visual Working Memory ◽  
Effect Size ◽  
Working Memory Capacity ◽  
Memory Capacity ◽  
Medium Effect ◽  
Full Spectrum ◽  
Small Effect Size ◽  
The Difference

Abstract Background Impaired working memory is a core cognitive deficit in both bipolar disorder and schizophrenia. Its study might yield crucial insights into the underpinnings of both disorders on the cognitive and neurophysiological level. Visual working memory capacity is a particularly promising construct for such translational studies. However, it has not yet been investigated across the full spectrum of both disorders. The aim of our study was to compare the degree of reductions of visual working memory capacity in patients with bipolar disorder (PBD) and patients with schizophrenia (PSZ) using a paradigm well established in cognitive neuroscience. Methods 62 PBD, 64 PSZ, and 70 healthy controls (HC) completed a canonical visual change detection task. Participants had to encode the color of four circles and indicate after a short delay whether the color of one of the circles had changed or not. We estimated working memory capacity using Pashler’s K. Results Working memory capacity was significantly reduced in both PBD and PSZ compared to HC. We observed a small effect size (r = .202) for the difference between HC and PBD and a medium effect size (r = .370) for the difference between HC and PSZ. Working memory capacity in PSZ was also significantly reduced compared to PBD with a small effect size (r = .201). Thus, PBD showed an intermediate level of impairment. Conclusions These findings provide evidence for a gradient of reduced working memory capacity in bipolar disorder and schizophrenia, with PSZ showing the strongest degree of impairment. This underscores the importance of disturbed information processing for both bipolar disorder and schizophrenia. Our results are compatible with the cognitive manifestation of a neurodevelopmental gradient affecting bipolar disorder to a lesser degree than schizophrenia. They also highlight the relevance of visual working memory capacity for the development of both behavior- and brain-based transdiagnostic biomarkers.

EUROPIUM OXALATE ION ASSOCIATION IN WATER

1966 ◽  
Vol 44 (24) ◽  
pp. 3057-3062 ◽  
Author(s):  
P. G. Manning
Keyword(s):  
Acetic Acid ◽  
Ionic Strength ◽  
Stability Constant ◽  
Stability Constants ◽  
Aqueous Phase ◽  
Sodium Acetate ◽  
Ion Association ◽  
Sodium Oxalate ◽  
Aqueous Sodium ◽  
Oxalate Ion

The partitioning of radiotracer 152/151Eu between aqueous sodium oxalate (Na2L) solutions and toluene solutions of thenoyltrifluoroacetone (HTTA) has been studied as a function of the oxalate concentration. The pH of the aqueous phase was controlled by means of sodium acetate – acetic acid mixtures and the ionic strength (I) by NaCl or NaClO4.At low ionic strengths (~0.05) and [L] ~10−4 M EuL+ formed, but at I = 0.95 and [L] ~10−3 M EuL2− also formed. Stability constants for the 1:1 and 1:2 (metal:ligand) complexes are reported.The magnitudes of the stepwise stability constant ratios are discussed.

Sign in / Sign up

Export Citation Format

Share Document