Electrolyte Molar Volumes at 273-373-K in Propylene Carbonate, N-Methylformamide, Formamide and Methanol: Their Relation to Solvent Compressibility. Ion Association Constants in Acetonitrile at 298-K

1986 ◽  
Vol 39 (12) ◽  
pp. 1959 ◽  
Author(s):  
GA Bottomley ◽  
MT Bremers
Keyword(s):  
Propylene Carbonate ◽  
Isothermal Compressibility ◽  
Ion Association ◽  
Ion Pair ◽  
Association Constants ◽  
Apparent Molar Volumes ◽  
Temperature Dependent ◽  
Liquid Sulfur ◽  
Molar Volumes ◽  
Ion Association Constants

Measurements have been made on several electrolytes of their apparent molar volumes at 25°C by dilatometry and typically from 0°C to 125°C by expansimetry in propylene carbonate, N- methylformamide, formamide, and methanol. The electrolyte limiting apparent molar volumes are shown to be linearly related to the temperature dependent isothermal compressibility in these solvents, as in water. Ion-pair equilibrium associated constants have been determined by volumetric means for NH4SCN, KSCN and ten other electrolytes in acetonitrile at 25°C and similarly for MgSO4 in water at 25°C. Less extensive apparent molar volume studies in water 0 to 160°C for high charge species and in liquid sulfur dioxide at 25° are also reported.

Octahedral cobalt(III) complexes in dipolar aprotic solvents. II. Association between cis- and trans-dichlorobisethylenediamine cobalt(III) cations,[Co en2 Cl2]+, and chloride and bromide ions in the solvents NN-dimethylformamide, dimethyl sulphoxide, and LVN-dimethylacetamide

1966 ◽  
Vol 19 (1) ◽  
pp. 43 ◽  
Author(s):  
WA Millen ◽  
DW Watts
Keyword(s):  
Spectrophotometric Method ◽  
Ion Pairs ◽  
Ion Association ◽  
Ion Pair ◽  
Association Constants ◽  
Dimethyl Sulphoxide ◽  
Aprotic Solvents ◽  
Ion Association Constants ◽  
Cis And Trans ◽  
Dipolar Aprotic Solvents

Ion association constants at 30� have been determined for the cis-[Co en, Cl2]+Cl- ion pair in NN-dimethylformamide (DMF), NN-dimethylacetamide (DMA), and at 20.0�, 25.0�, and 30.0� in dimethyl sulphoxide (DMSO), by a spectrophotometric method. Association constants for the cis-[Co en2 Cl2]+Br- and the trans- [Co en2 Cl2]+Cl- ion pairs have also been determined in DMF at 30�.

Octahedral cobalt(III) complexes in dipolar aprotic solvents. VI. Spectrophotometric determination of ion association of halide ions with cis-chlorodimethylformamidebisethylenediaminecobalt(III) ion and cis-chlorobromobisethylenediaminecobalt(III)ion in anhydrous NN-dimethylformamide

1966 ◽  
Vol 19 (6) ◽  
pp. 969 ◽  
Author(s):  
IR Lantzke ◽  
DW Watts
Keyword(s):  
Ion Association ◽  
Cobalt Complexes ◽  
Complex Salt ◽  
Ion Pair ◽  
Association Constants ◽  
Halide Ions ◽  
Kcal Mole ◽  
Ion Association Constants ◽  
Dipolar Aprotic Solvents

Using a spectrophotometric technique the ion association constants for three systems of octahedral cobalt complexes and halide ions have been determined at three temperatures in NN-dimethylformamide. The values of K, ΔH�, and ΔS� for each system have been calculated. At 30� they are as follows: cis-[CoCl(DMF) en2]2+ + Cl- ↔ ion pair K=1.51�0.03 x 104 1.mole-1(ΔH0= 0.93 � 0.02 kcal mole-1,ΔS�= 22.l+0.4 e.u) cis-[CoCl(DMF) en2]2++2Cl- ↔ ion triplet K= 1.21�0.05 X 106 1.2 mole-2(ΔH�=-3.8�0.lkcal mole-1, ΔS�=15.41� 0.5 e.u) cis-[CoCl(DMF) en2]2++Br- ↔ ion pair K= 9.20�0.18 X 103 1.1 mole-1(ΔH�=-7.2�0.lkcal mole-1, ΔS�=42� 1.0 e.u) cis-[CoBrCl en2]+ + Br- ↔ ion pair K = 690�l41. mole-1 (ΔH� = 1.27�0.03 kcal mole-1, ΔS�= 8.8�0.2 e.u.) The dependence of the measured K, the association constant, on the wavelength of measurement, small amounts of water in the solvent, and the anion of the complex salt, has also been investigated.

scholarly journals Volumetric Properties in the NaAsO2 + H2O System at Temperature from 283.15 to 363.15 K and Atmospheric Pressure

2020 ◽  
Vol 2020 ◽  
pp. 1-7
Author(s):  
Hongfang Hou ◽  
Wanjing Cui ◽  
Jiaojiao Chen ◽  
Lingzong Meng ◽  
Yafei Guo ◽  
...  
Keyword(s):  
Thermal Expansion ◽  
Molar Volume ◽  
Thermal Expansion Coefficient ◽  
Expansion Coefficient ◽  
Apparent Molar Volume ◽  
Correlation Coefficients ◽  
Apparent Molar Volumes ◽  
Temperature Dependent ◽  
Molar Volumes ◽  
Experimental Values

Densities of sodium arsenite (NaAsO2) aqueous solution with the molality varied from 0.19570 to 1.94236 mol·kg−1 at temperature intervals of 5 K from 283.15 to 363.15 K and 101 ± 5 kPa were measured by a precise Anton Paar Digital vibrating-tube densimeter. Apparent molar volumes (VΦ) and thermal expansion coefficient (α) were obtained on the basis of experimental data. The 3D diagram of apparent molar volume against temperature and molality and the diagram of thermal expansion coefficient against molality were generated. According to the Pitzer ion-interaction equation of the apparent molar volume model, the Pitzer single-salt parameters (βM,X0υ, βM,X1υ, βM,X2υ, and CM,Xυ, MX = NaAsO2) and their temperature-dependent correlation F(i, p, T) = a1 + a2ln (T/298.15) + a3(T − 298.15) + a4/(620 − T) + a5/(T − 227) (where T is temperature in Kelvin and ai are the correlation coefficients) for NaAsO2 were obtained for the first time. The predictive apparent molar volumes agree well with the experimental values, and those results indicated that the single-salt parameters and the temperature-dependent formula are reliable.

scholarly journals When spectroscopy fails: The measurement of ion pairing

2006 ◽  
Vol 78 (8) ◽  
pp. 1571-1586 ◽  
Author(s):  
Glenn Hefter
Keyword(s):  
Metal Ion ◽  
Chemical Speciation ◽  
Ion Pairs ◽  
Ion Association ◽  
Ion Pair ◽  
Association Constants ◽  
Spectroscopic Techniques ◽  
Association Equilibria ◽  
Solvent Molecules ◽  
Contact Ion Pairs

Spectroscopic techniques such as UV/vis, NMR, and Raman are powerful tools for the investigation of chemical speciation in solution. However, it is not widely recognized that such techniques do not always provide reliable information about ion association equilibria. Specifically, spectroscopic measurements do not in general produce thermodynamically meaningful association constants for non-contact ion pairs, where the ions are separated by one or more solvent molecules. Such systems can only be properly quantified by techniques such as dielectric or ultrasonic relaxation, which can detect all ion-pair types (or equilibria), or by traditional thermodynamic methods, which detect the overall level of association. Various types of quantitative data are presented for metal ion/sulfate systems in aqueous solution that demonstrate the inadequacy of the major spectroscopic techniques for the investigation of systems that involve solvent-separated ion pairs. The implications for ion association equilibria in general are briefly discussed.

scholarly journals Preparation of Some Novel Copper(I) Complexes and their Molar Conductances in Organic Solvents

2009 ◽  
Vol 64 (3-4) ◽  
pp. 269-272 ◽  
Author(s):  
Dip Singh Gill ◽  
Dilbag Rana
Keyword(s):  
Organic Solvents ◽  
Ion Association ◽  
Solvent System ◽  
Molar Conductance ◽  
Association Constants ◽  
Complex Ions ◽  
Ion Association Constants ◽  
Conductance Data ◽  
Strong Electrolytes ◽  
Reference Electrolyte

Abstract Attempts have been made to prepare some novel copper(I) nitrate, sulfate, and perchlorate complexes. Molar conductances of these complexes have been measured in organic solvents like acetonitrile (AN), acetone (AC), methanol (MeOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), and dimethylsulfoxide (DMSO) at 298 K. The molar conductance data have been analyzed to obtain limiting molar conductances (λ0) and ion association constants (KA) of the electrolytes. The results showed that all these complexes are strong electrolytes in all organic solvents. The limiting ionic molar conductances (λo± ) for various ions have been calculated using Bu4NBPh4 as reference electrolyte. The actual radii for copper(I) complex ions are very large and different in different solvents and indicate some solvation effects in each solvent system

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