The thermodynamics of aqueous borate solutions. II. Mixtures of boric acid with calcium or magnesium borate and chloride

Potentials for the cell without liquid juction

Thermodynamic Study of the NaCl + Na2SO4 + H2O System by Emf Measurements at Four Temperatures

Activity coefficients for sodium chloride in the NaCl + Na₂SO₄ + H₂O ternary system were determined from emf measurements of the cell

The effect of pressure on the dissociation of boric acid and sodium borate ion pairs at 25°C

A high pressure UV-visible spectrophotometer was used to determine the dissociation constant of boric acid using an indicator technique. The measurements were made at 25°C and at ionic strengths of 0.1 and 1.0m over a pressure range of 1 to 2000 atm. Extrapolation to I=0 gave a thermodynamic dissociation constant of 5.16×10^–10 at 1 atm. The pressure dependence yielded a partial molal volume change of –28.9 and –31.8 cm³-mol^–1 and a compressibility change of –3.1 and –4.8×10^–3 cm³-mol^–1-atm^–1 for the dissociation at I=0.1 and 1.0m, respectively. The association constant for the formation of the sodium borate ion pair was determined by comparing the acid constants in tetramethylammonium chloride to those in sodium chloride solutions. Extrapolation to I=0 yielded a K_A for [NaB(OH)₄] of 0.64 at 1 atm. The pressure dependence of K_A gave and for the formation of the ion pair.     

Chemical modification of dispersed silica by pyrimidine derivatives

Results are given of the chemical modification of silicas containing and groups on their surface by pyridimidines in the gaseous phase. IR spectroscopy and field desorption mass spectrometric methods were used to obtain information on the structure of the surface compounds prepared. Possible reaction schemes are suggested. The high hydrolytic stability of some of the immobilized hydroxypyrimidines has been established.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 4, pp. 495–499, July–August, 1986.     

Determination of activity coefficients using a flow EMF method. 1. HCl in methanol-water mixtures at 25, 35 and 45°C

A method to determine activity coefficients of electrolytes in mixed solvent is described which makes use of ion-selective electrode(s) (ISE) and in which a concentrated electrolyte solution is continuously added. Activity coefficients for HCl in methanol-water mixtures containing 0, 10, 20, 30, 50, 70, and 90 weight percent methanol at 25, 35 and 45°C were calculated using the Pitzer equation, and the electromotive force (emf) data of the cell: The experimental results agree well with literature values indicating that the proposed method is procise and reliable.     

Solubility of Oxygen in Some 1-1, 2-1, 1-2, and 2-2 Electrolytes as a Function of Concentration at 25°C

The solubility of oxygen has been measured in a number of electrolytes [(LiCl, KCl, RbCl, CsCl, NaF, NaBr, NaI, NaNO₃, KBr, KI, KNO₃, CaCl₂, SrCl₂, BaCl₂, Li₂SO₄, K₂SO₄, Mn(NO₃)₃)] as a function of concentration at 25°C. The solubilities, mol (kg-H₂O)^–1, have been fitted to a function of the molality m (standard deviation < 3mol-kg^–1)

Aqueous Geochemistry of Rare Earth Elements and Yttrium. XII: Potentiometric Stability Constant Determination of Bis-Tris Complexes with La, Nd, Eu, Gd, Yb, Dy, Er, Lu, and Y

Conditional stability constants of 2-[bis(2-hydroxyethyl)amino]-2(hydroxymethyl)-1,3-propanediol (BT) complexes of trivalent rare earth element (Ln) ions (La, Nd, Eu, Gd, Yb, Dy, Er, Lu) and Y were determined potentiometrically in aqueous NaCl solutions at 30°C and 0.1 M ionic strength. Least-squares fitting shows that, at <0.04 molal BT, the complex LnBT³⁺ is dominant, with LnBT₂ ³⁺ forming a secondary complex, where:

Binuclear Cu(II) and Ni(II) Complexes with Schiff Bases—the Products of Condensation of Amino Alcohols with 2-Phenylhydrazone 1-Phenylbutane-1,2,3-Trione: Synthesis and Magnetic Properties

The binuclear complexes of Cu²⁺ and Ni²⁺ with a new ligand system obtained through condensation of amino alcohols with 2-phenylhydrazone 1-phenylbutane-1,2,3-trione were synthesized. The compositions and structures of ligands and complexes were determined using elemental analysis, IR and NMR spectroscopy and magnetochemistry. The nickel complexes were found to be diamagnetic; in the copper complexes, substantial antiferromagnetic exchange interaction was observed (for Cu²⁺ complexes with n = 2 and 3, 2J is equal to –396 and –393 cm^–1, respectively). The structure of the exchange fragment is discussed.     

Stability constants of iron(III) borate complexes

The ultraviolet absorbance data from experiments conducted at constant pH and total iron concentration but variable B(OH)₃ concentration were used to determined the stability constants of FeB(OH) ₄ ²⁺ and Fe[B(OH)_{4 2} ⁺ at 25°C and an ionic strength of 0.68. The estimates obtained were *₁ = 1.0 ± 0.2 × 10^–2 and *₂ = 2 ± 1 × 10^–5, respectively (uncertainties are two times the standard error of the estimates). A calculation of the extent of iron(III) borate formation in ocean water at pH 8.2 shows that iron(III) borates are not a significantly large component of iron(III) speciation in seawater.     

Comprehensive Investigation of Yttrium and Rare Earth Element Complexation by Carbonate Ions Using ICP–Mass Spectrometry

Carbonate stability constants for yttrium and all rare earth elements have been determined at 25°C and 0.70 molal ionic strength by solvent exchange and inductively coupled plasma–mass spectrometry (ICP–MS). Measured stability constants for the formation of and from M³⁺ are in good agreement with previous direct measurements, which involved the use of radio-chemical techniques and trivalent ions of Y, Ce, Eu, Gd, Tb, and Yb. Direct ICP–MS measurements of and formation constants are also in general agreement with modeled stability constants for the metals La, Pr, Nd, Sm, Dy, Ho, Er, Tm, and Lu, based on linear-free energy relationship (LFER). The experimental procedures developed in this work can be used for assessing the complexation behavior of other geochemically important ligands such as phosphate, sulfate, and fluoride.     

Stereospezifische Synthese und Konfiguration der 1-Amino-und 1-Anilino-3-dialkylamino-1,2-diphenylpropane

Zusammenfassung Durch Reduktion von Dialkylamiden der diastereomeren 3-Anilino- und 3-Amino-2,3-diphenylpropansäuren mit LiAlH₄ wurde die stereospezifische Synthese von 1-Anilino-bzw. 1-Amino-3-dialkylamino-1,2-diphenylpropanen verwirklicht. Die Konfiguration der erhaltenen Verbindungen wurde durch spektralanalytische Aussagen über den Charakter der Wasserstoff-brückenbindung vom Typ bestätigt.Mit 1 Abbildung     

Effect of ionic strength and ionic interactions on the oxidation of Fe(II)

The rates of oxidation of Fe(II) in NaCl and NaClO ₄ solutions were studied as a function of pH (6 to 9), temperature (5 to 25°C), and ionic strength (0 to 6m). The rates are second order with respect to [H⁺] or [OH^–] and independent of ionic strength and temperature. The overall rate of the oxidation is given by

The effect of pressure on the ionization of water at various temperatures from molal-volume data1

The apparent molal volumes of dilute (0.002 to 1.0m) aqueous HCl and NaOH solutions have been determined at 0, 25, and 50°C and NaCl solutions at 50°C. The partial molal volumes ( ) of HCl, NaOH, and NaCl solutions have been determined from these apparent molal volumes and other reliable data from the literature. The partial-molal-volume changes ( ) for the ionization of water, H₂OH⁺+OH^–, have been determined from 0 to 50°C and 0 to 1m ionic strength from the partial molal volumes of HCl, NaOH, NaCl, and H₂O. The partial molal compressibilities ( for HCl, NaOH, NaCl, and H₂O have been estimated from data in the literature and used to determine the partial molal compressibility changes ( ) for the ionization of water from 0 to 50°C and 0 to 1m ionic strength. The effect of pressure on the ionization constant of water has been estimated from partial-molal-volume and compressibility changes using the relation from 0 to 50°C and 0 to 2000 bars. The results agree very well with the directly measured values.Contribution Number 1548 from the University of Miami.     

Kinetics and mechanism of osmium(VIII)-catalyzed oxidation of hypophosphite by hexacyanoferrate(III) in aqueous alkali

The kinetics of osmium(VIII)-catalyzed oxidation of hypophosphite with hexacyanoferrate(III) in alkaline medium has been studied. The rate is independent of the concentration of the oxidant. The order with respect to hydroxide ion is variable. Rate law (1) conforms with the experimental observations.

Action of diisobutylaluminum hydride on enamines

Summary Diisobutylaluminum hydride adds to enamines with the formation of compounds containing the grouping , the thermal decomposition of which gives the corresponding olefins in good yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1695–1697, September, 1964     

O-H ... O(S) hydrogen bonds in 2-hydroxy(thio)benzamides. Survey of spectroscopic and structural data

Summary From a survey of spectroscopic and structural data of six corresponding 2-hydroxybenzamides and 2-hydroxythiobenzamides (amide, N-methylamide, N,N-dimethylamide, piperidide, morpholide, 2,6-dimethylpiperidide) remarkable similarities between O(N)-H ... O and O(N)-H ... S hydrogen-bonds are obtained, concerning both, hydrogen-bond patterns and hydrogen-bond strengths. In dilute solution the OH groups of all compounds are intramolecularly associated to the (thio)carbonyl O (S) atoms with distinctly larger hydrogen-bond strengths for primary and secondary amides [ (O-H)=2950–3020 cm^–1, (OH)=12.16–11.99 ppm] and thioamides [ (O-H)=2960–3000 cm^–1, (OH)=11.65–11.13 ppm], than for tertiary amides [ (O-H)=3200–3250 cm^–1, (OH)=9.95–8.95 ppm] and thioamides [ (O-H)=3245–3330 cm^–1, (OH)=8.09–7.06 ppm]. In the solid state, the OH groups of the primary and secondary (thio)amides are also engaged in rather strong intramolecular O-H ... O=C [O ... O=2.51 Å, (O-H)=2700–2750 cm^–1] and O-H ... S=C [O ... S=2.90–2.94 Å, (O-H)=2700–2840 cm^–1] hydrogen-bonds; thetrans-NH groups of the primary (thio)amides and the NH groups of the secondary (thio)amides connect the molecules to N-H ... O-H [N ... O=2.93–3.10 Å, (N-H)=3319–3407 cm^–1] hydrogen-bonded chains; the remainingcis-NH groups of the primary (thio)amides give rise to eight-membered cyclic dimers via N-H ... O=C [N ... O=2.93 Å, (N-H)=3226 cm^–1] and N-H ... S=C [N ... S=3.46–3.47 Å, (N-H)=3233–3277 cm^–1] hydrogen-bonds. Contrary, the OH groups of the tertiary (thio)amides are intermolecular associated in the solid state and link the molecules to O-H ... O=C [O ... O=2.63–2.75 Å, (O-H)=3075–3135 cm^–1] and O-H ... S=C [O ... S=3.18–3.26 Å, (O-H)=3130–3190 cm^–1] hydrogen-bonded chains.

---

O-H ... O(S)-Wasserstoffbrückenbindungen in 2-Hydroxy(thio)benzamiden. Ein Überblick über spektroskopische und strukturelle Daten

Zusammenfassung Aus einer Zusammenstellung von spektroskopischen und strukturellen Daten von sechs entsprechenden 2-Hydroxybenzamiden und 2-Hydroxythiobenzamiden (Amid, N-Methylamid, N,N-Dimethylamid, Piperidid, Morpholid, 2,6-Dimethylpiperidid) ergeben sich bemerkenswerte Analogien zwischen O(N)-H ... O und O(N)-H ... S H-Brücken, die sowohl die H-Brücken-Muster als auch die H-Brücken-Stärken betreffen. In verdünnter Lösung sind die OH-Gruppen aller Verbindungen intramolekular mit den O(S)-Atomen der (Thio)Carbonylgruppen assoziiert, wobei die H-Brücken bei den primären und sekundären Amiden [ (O-H)=2950–3020 cm^–1, (OH)=12.16–11.99 ppm] und Thioamiden [ (O-H)=2960–3060 cm^–1, (OH)=11.65–11.13 ppm] deutlich stärker sind, als bei den tertiären Amiden [ (O-H)=3200–3250 cm^–1, (OH)=9.95–8.95 ppm] und Thioamiden [ (O-H)=3245–3330 cm^–1, (OH)=8.09–7.06 ppm]. Im Festkörper weisen die primären und sekundären (Thio)Amide ebenfalls sehr starke intramolekulare O-H ... O=C [O ... O=2.51 Å, (O-H)=2700–2750 cm^–1] und O-H ... S=C [O ... S=2.90–2.94 Å, (O-H)=2700–2840 cm^–1] H-Brücken auf; dietrans-NH-Gruppen der primären (Thio)Amide und die NH-Gruppen der sekundären (Thio)Amide verknüpfen die Moleküle über N-H ... O-H H-Brücken [N ... O=2.93–3.10 Å, (N-H)=3318–3407 cm^–1] zu Ketten; die verbleibendencis-NH-Gruppen der primären (Thio)Amide bilden zyklische, über N-H ... O=C [N ... O=2.93 Å, (N-H)=3226 cm^–1] und N-H ... S=C [N ... S=3.46–3.47 Å, (N-H)=3233–3277 cm^–1] H-Brücken gebundene, 8-Ring-Dimere. Im Gegensatz dazu sind die OH-Gruppen der tertiären (Thio)Amide im Festkörper intermolekular assoziiert und verknüpfen die Moleküle über O-H ... O=C [O ... O=2.63–2.75 Å, (O-H)=3075–3135 cm^–1] und O-H ... S=C [O ... S=3.18–3.26 Å, (O-H)=3130–3190 cm^–1] H-Brücken zu Ketten.

     

Oxidation of chromium(III) by alkaline hexacyanoferrate(III)

Alkaline hexacyanoferrate(III) oxidation of freshly prepared solutions of Cr^III (pH>12) at 27°C follows the rate law, Equation 1:

Magnetite solubility and phase stability in alkaline media at elevated temperatures

A platinum-lined flowing autocláve facility was used to investigate the solubility behavior of magnetite (Fe₃O₄) in alkaline sodium phosphate and ammonium hydroxide solutions between 21 and 288°C. Measured iron solubilities were interpreted via a Fe(II)/Fe(III) ion hydroxo-, phosphato-, and ammino-complexing model and thermodynamic functions for these equilibria were obtained from a least-squares analysis of the data. A total of 14 iron ion species were fitted. Complexing equilibria are reported for 8 new species: Fe(OH)(HPO₄)^–, Fe(OH)₂(HPO₄)^2–, Fe(OH)₃(HPO₄)^2–, Fe(OH)(NH₃)⁺, Fe(OH)₂(PO₄)^3–, Fe(OH)₄(HPO₄)^3–, Fe(OH)₂(H₂PO₄)^–, and Fe(OH)₃(H₂PO₄)^3–. At elevated temperatures, hydrolysis and phosphato complexing tended to stabilize Fe(III) relative to Fe(II), as evidenced by free energy changes fitted to the oxidation reactions.

Komplexverbindungen von Germaniumsäure mit ÄDTE und ÄDTE-Analogen, 1. Mitt.: Äthylendiamintetraessigsäure

Zusammenfassung Die Verbindung GeY · 2 H₂O wird nach einem Verfahren dargestellt, das die Verwendung von flüchtigem GeCl₄ vermeidet und direkt von Germaniumsäure-Lösungen ausgeht. Der Komplex, der analysenrein anfällt, wird thermogravimetrisch untersucht. In Wasser gelöst, erweist er sich als einbasige Säure, H[Ge(OH)Y]. Die Dissoziationskonstante der komplexen Säure wird potentiometrisch bestimmt:K _c =3,99 · 10^–3 (pK _c =2,40). Die Stabilitätskonstanten der komplexen Säure sowie des komplexen Anions werden ermittelt: =6,27 · 10⁴ (log =4,80); =3,34 · 10⁴ (log =4,52) (25°C; Ionenstärke 0,1m).

---

The complex compound GeY · 2 H₂O is prepared directly from germanic acid solutions, avoiding volatile GeCl₄. It has been submitted to thermogravimetric analysis. Dissolved in water, it proves to be a monobasic acid, H[Ge(OH)Y]. The dissoziation constant of the complex acid is determined potentiometrically:K _c =3,99 · 10^–3 (pK _c =2,40). The stability constants of the complex acid as well as of the complex anion are evaluated: =6,27 · 10⁴ (log =4,80); =3,34 · 10⁴ (log =4,52), at 25°C; ionic strength 0,1m.

---

---

Mit 4 Abbildungen

---

Herrn Prof. Dr.J. W. Breitenbach zum 60. Geburtstag gewidmet.     

Dissociation Constants of Protonated Cysteine Species in NaCl Media

The sulfur-containing biomolecule, cysteine has a role in physiological and natural environment because of its strong interactions with metals. To understand these interactions of metals with cysteine, one needs reliable dissociation constants for the protonated cysteine species [ CH(CH₂SH)COOH; H₃B⁺]. The values of dissociated constants, p , for protonated cysteine species (H₃B⁺ H⁺ + H₂B, K ₁; H₂B H⁺ + HB^–,K ₂; HB^– H⁺ + B^2–,K ₃) were determined from potentiometric measurements in NaCl solutions as a function of ionic strength, 0.5–6.0 mol-(kgH₂O)^–1 and between 5, and 45°C. The equations