Acceptor Numbers for Binary Mixtures of Dipolar Aprotic Solvents with Methanol

1994 ◽  
Vol 59 (6) ◽  
pp. 1349-1355 ◽  
Author(s):  
Malgorzata Podsiadla ◽  
Jadwiga Rzeszotarska ◽  
Marek K. Kalinowski

Using bis(cyano)bis(9,10-phenanthroline)iron(II) as solvatochromic indicator, the acceptor numbers, AN, were determined for binary mixtures of benzene, benzonitrile, acetonitrile, acetone, N,N-dimethylformamide, dimethyl sulfoxide and hexamethylphosphoric triamide with methanol. Deviations from linearity of the plots of AN values against the molar fraction of the components were interpreted both in terms of changes in solvent liquid structure and in cathegories of preferential solvation.

1994 ◽  
Vol 59 (10) ◽  
pp. 2201-2208 ◽  
Author(s):  
Jadwiga Rzeszotarska ◽  
Przemyslaw Ranachowski ◽  
Marek K. Kalinowski

Solvent effect on the visible absorption spectrum of (acetylacetonato)(N,N,N',N'-tetramethylethylene-diamine)copper(II) was applied to estimate DN, the donor numbers of the binary mixtures of dimethyl sulfoxide with a series of other dipolar aprotic solvents. It was found that resulting DN values may be treated as explanatory parameters in the description of the mixed solvent effect on the stability constants of complexes formed by some macrocyclic ligands with univalent cations.


1985 ◽  
Vol 50 (11) ◽  
pp. 2493-2508 ◽  
Author(s):  
Petr Kyselka ◽  
Zdeněk Havlas ◽  
Ivo Sláma

Solvation of Li+, Be2+, Na+, Mg2+, and Al3+ ions has been studied in binary mixtures with dimethyl sulphoxide, dimethylformamide, acetonitrile and water, and in ternary mixtures of the organic solvents with water. The CNDO/2 quantum chemical method was used to calculate the energies of solvation, molecular structures and charge distributions for the complexes acetonitrile...ion (1:1, 2:1, 4:1), dimethyl sulphoxide...ion (1:1), dimethylformamide...ion (1:1), and acetonitrile (dimethyl sulphoxide, dimethylformamide)...ion...water (1:1:1).


1983 ◽  
Vol 36 (10) ◽  
pp. 1923 ◽  
Author(s):  
JMB Harrowfield ◽  
L Spiccia ◽  
DW Watts

Previous work on the reduction of a series of cobalt(III) complexes by iron(II) in dipolar aprotic solvents and in aqueous mixtures has been extended to reduction by copper(I). The greater stability of copper(I) to disproportionation in these media has permitted the study of the reduction of CoF(NH3)52+ and Co(HCOO)(NH3)52+ in range of solvents over a number of temperatures with a precision not possible in previous studies in water. The results are consistent with an inner-sphere mechanism in which the copper(I) reductant is preferentially solvated by dimethyl sulfoxide to the exclusion of water in mixed solvents.


1983 ◽  
Vol 36 (9) ◽  
pp. 1753 ◽  
Author(s):  
Jr MK Chantooni ◽  
IM Kolthoff ◽  
G Roland

Stability constants, Kf(LK+) and Kf(LKX) = [LKX]/[L][KX] at 25� in the dipolar aprotic solvents acetone (Me2CO), acetonitrile (MeCN), propylene carbonate (pc), N,N-dimethylformamide (HCONMe2), dimethyl sulfoxide (Me2SO), as well as in the alcohols, methanol (MeOH), isopropyl alcohol (Pr1OH), and butan -1-ol (BuOH) have been determined, L being bis(4,4'(5')-t-buty1benzo)-18- crown-6 (di(BuBo)-18-cr-6). This crown is considerably more lipophylic than is dibenzo-18-crown-6. Values of Kf(LKX) have been found from values of Kf(LK+), KA(KX) and KA(LKX). Transfer activity coefficients, Me2COγS, have been calculated (based on the Parker proposal that γ(Ph4As+) = γ(BPh4-) between acetone and the various solvents used of K+, Br-, ClO4-, P1- (picrate), LK+, KX, and LKX. It is found that K+ is more strongly solvated in Me2CO than in the other aprotic solvents of low donicity. The reverse is true between Me2CO and HCONMe2 or Me2SO (even after correcting for the Born effect).


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