The ionization and dissociation of triphenylmethyl chloride in 1,2-dichloroethane-styrene mixtures

1978 ◽  
Vol 31 (11) ◽  
pp. 2445 ◽  
Author(s):  
SS Bos ◽  
FE Treloar
Keyword(s):  
Mercuric Chloride ◽  
Cationic Polymerization ◽  
Equilibrium Constants ◽  
Ion Pairs ◽  
Free Ions

Triphenylmethyl chloride with mercuric chloride ionizes and dissociates in 1,2-dichloroethane and 1,2-dichloroethane-styrene mixtures into ion pairs and free ions. The values of the equilibrium constants for ionization to ion pairs and the subsequent dissociation of these show that the free ions are preferentially solvated by the added styrene. The consequences of this for the cationic polymerization of styrene are briefly discussed.

A comparison of acetone and poly(propylene glycol) as solvents for lithium triflate and lithium perchlorate

1991 ◽  
Vol 69 (12) ◽  
pp. 1980-1984 ◽  
Author(s):  
James R. Stevens ◽  
Per Jacobsson
Keyword(s):  
Propylene Glycol ◽  
Ion Pairs ◽  
Lithium Perchlorate ◽  
Lithium Triflate ◽  
Free Ions ◽  
Lower Dielectric Constant ◽  
Current Controversy ◽  
Raman Modes ◽  
Poly Propylene ◽  
Key Words Acetone

Solutions of LiCF3SO3 and LiClO4 in acetone and in poly(propylene glycol) (PPG 400 and PPG 4000) have been compared by studying the nondegenerate, symmetric stretch (A1,SO3) and (A1,ClO4) Raman modes. The Raman spectra contain bands due to the symmetric stretching motion of the "free" anion and due to the symmetric stretching motion of anions in ion aggregates. It is concluded that "free" ions, ion pairs, triplets, and aggregates are present. Although PPG has a much lower dielectric constant, it is a better solvent for these salts than the dipolar aprotic acetone. These findings have ramifications on the current controversy of whether "free" ions are present at all in polyether–salt complexes such as PPG 4000/LiCF3SO3. Key words: acetone, poly(propylene glycol), lithium triflate, lithium perchlorate, Raman.

The absolute rate constants of anionic propagation by free ions and ion-pairs of living polystyrene

Polymer ◽  
1964 ◽  
Vol 5 ◽  
pp. 54-56 ◽  
Author(s):  
D.N. Bhattacharyya ◽  
C.L. Lee ◽  
J. Smid ◽  
M. Szwarc
Keyword(s):  
Rate Constants ◽  
Ion Pairs ◽  
Absolute Rate ◽  
Free Ions ◽  
The Absolute

Cationic polymerization of isoprene: Initiation by complexes of titanium chloride with halogenoacetic acids

1979 ◽  
Vol 44 (4) ◽  
pp. 1262-1272 ◽  
Author(s):  
Bohumír Matyska ◽  
Ludmila Petrusová ◽  
Karel Mach ◽  
Miroslav Švestka
Keyword(s):  
Electric Conductivity ◽  
Cationic Polymerization ◽  
Kinetic Data ◽  
Trichloroacetic Acid ◽  
Polymerization Rate ◽  
Ester Bond ◽  
Titanium Chloride ◽  
Active Centers ◽  
Butyl Esters ◽  
Free Ions

Polymerization of 2-methyl-1,3-butadiene (isoprene), initiated by titanium chloride in combination with trifluoro- and trichloroacetic acid and their t-butyl esters as coinitiators, was studied in benzene, 1,2-dichlorobenzene and heptane at 20 °C. Curves of the dependence polymerization rate vs coinitiator concentrations exhibit in the first two media a minimum and a maximum, those in heptane exhibit an inflex only. This is due to the fact that the acids and the esters are partly consumed to carboxylate TiCl4 and to form mono- and dicarboxylates of titanium chloride. Other products are either HCl or the corresponding alkylchlorides whose co-catalytic activity is very low. It follows from kinetic data and from electric conductivity and infrared spectra measurements that active centers in the polymerization are complexes of oligoesters of halogenoacetic acids with TiCl4 and its carboxylates, in which the ester bond is either considerably polarized or dissociated. Free ions are formed during the polymerization, too, contributing to changes of electric conductivity; however, they do not influence the polymerization rate directly.

scholarly journals Ion association in water solution of soil and vadose zone of chestnut saline solonetz as a driver of terrestrial carbon sink

Solid Earth ◽  
2016 ◽  
Vol 7 (2) ◽  
pp. 415-423 ◽  
Author(s):  
Abdul-Malik A. Batukaev ◽  
Anatoly P. Endovitsky ◽  
Andrey G. Andreev ◽  
Valery P. Kalinichenko ◽  
Tatiana M. Minkina ◽  
...  
Keyword(s):  
Calcium Carbonate ◽  
Vadose Zone ◽  
Carbon Sink ◽  
Water Solution ◽  
Equilibrium Constants ◽  
Ion Pairs ◽  
Material Balance ◽  
Ion Association ◽  
Free Form ◽  
Carbonate Equilibrium

Abstract. The assessment of soil and vadose zone as the drains for carbon sink and proper modeling of the effects and extremes of biogeochemical cycles in the terrestrial biosphere are the key components to understanding the carbon cycle, global climate system, and aquatic and terrestrial system uncertainties. Calcium carbonate equilibrium causes saturation of solution with CaCO3, and it determines its material composition, migration and accumulation of salts. In a solution electrically neutral ion pairs are formed: CaCO30, CaSO40, MgCO30, and MgSO40, as well as charged ion pairs CaHCO3+, MgHCO3+, NaCO3−, NaSO4−, CaOH+, and MgOH+. The calcium carbonate equilibrium algorithm, mathematical model and original software to calculate the real equilibrium forms of ions and to determine the nature of calcium carbonate balance in a solution were developed. This approach conducts the quantitative assessment of real ion forms of solution in solonetz soil and vadose zone of dry steppe taking into account the ion association at high ionic strength of saline soil solution. The concentrations of free and associated ion form were calculated according to analytical ion concentration in real solution. In the iteration procedure, the equations were used to find the following: ion material balance, a linear interpolation of equilibrium constants, a method of ionic pairs, the laws of initial concentration preservation, operating masses of equilibrium system, and the concentration constants of ion pair dissociation. The coefficient of ion association γe was determined as the ratio of ions free form to analytical content of ion γe = Cass∕Can. Depending on soil and vadose zone layer, concentration and composition of solution in the ionic pair's form are 11–52 % Ca2+; 22.2–54.6 % Mg2+; 1.1–10.5 % Na+; 3.7–23.8 HCO3−, 23.3–61.6 % SO42−, and up to 85.7 % CO32−. The carbonate system of soil and vadose zone water solution helps to explain the evolution of salted soils, vadose and saturation zones, and landscape. It also helps to improve the soil maintenance, plant nutrition and irrigation. The association of ions in soil solutions is one of the drivers promoting transformation of solution, excessive fluxes of carbon in the soil, and loss of carbon from soil through vadose zone.

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