Isotope Effects of Water Molecules on the Hydration of Alkali Metal and Halide Ions

2001 ◽  
Vol 74 (11) ◽  
pp. 2011-2017 ◽  
Author(s):  
Masahisa Kakiuchi
Keyword(s):  
Alkali Metal ◽  
Isotope Effects ◽  
Water Molecules ◽  
Halide Ions

Extrem asymmetrisch gebundene Wassermoleküle-Kristallstrukturen von Sr(OH)Cl · 4 H2O, Sr(OH)Br · 4 H2O und Ba(OH)I·4 H2O / Extremely Asymmetrically Bound Water Molecules-Crystal Structures of Sr(OH)Cl · 4 H2O, Sr(OH)Br · 4 H2O, and Ba(OH)I·4 H2O

1991 ◽  
Vol 46 (10) ◽  
pp. 1279-1286 ◽  
Author(s):  
Thomas Kellersohn ◽  
Konrad Beckenkamp ◽  
Heinz Dieter Lutz
Keyword(s):  
Crystal Structures ◽  
Bound Water ◽  
Structure Type ◽  
Water Molecules ◽  
Halide Ions ◽  
Weak Hydrogen Bond ◽  
Scanning Calorimetry ◽  
Unknown Structure ◽  
Stretching Vibrations ◽  
Strong Distortion

The crystal structures of isotypic Sr(OH)Cl ·4 H2O, Sr(OH)Br·4 H2O, and Ba(OH)I·4 H2O are reported. The title compounds crystallize in a hitherto unknown structure type, space group PĪ, Z = 2. The final R values obtained are 0.0261, 0.069, and 0.062, respectively. The coordination of the metal ions is monocapped square antiprismatic with 7 H2O, 1 OH- and 1 halide ion. The halide ions separate metal/water/hydroxide layers. Each of the four crystallographically different water molecules serves as donor for one very strong and one very weak hydrogen bond and, hence, is extremely asymmetrically bound. Owing to this strong distortion, the largest one known so far, the OH stretching vibrations of the H2O molecules are intramolecularly decoupled as shown from vibrational spectra. The enthalpies of dehydration obtained from differential scanning calorimetry are reported.

Radiothermal radiation method for aqueous solutions

2021 ◽  
Author(s):  
L.A. Morozova ◽  
S.V. Savel’ev
Keyword(s):  
Dielectric Properties ◽  
Alkali Metal ◽  
Thermal Radiation ◽  
Aqueous Solutions ◽  
Physical Properties ◽  
Dielectric Constants ◽  
Water Molecules ◽  
Absorption Coefficients ◽  
Basic Substance ◽  
High Dilutions

For the first time, an ultra-high-sensitivity method for measuring radio-thermal radiation was developed and used in practice in order to establish the difference in the physical properties of aqueous solutions of substances in the millimeter region of the spectrum. The method is used to study the dynamics of the dielectric properties of aqueous solutions depending on the composition of the base substance and its concentration. The dynamics of dielectric properties establishes a one-to-one correspondence between the number and concentration of ions of the dissolved basic substance contained in water and the number of water molecules involved in cooperative interaction, which gives a consistent microscopic picture of ion-water cooperative interactions in the studied aqueous solutions of K2SO4 and Cs2SO4. The density of water molecules perturbed by the ions of the base substance contained in the hydration shell at normal concentrations is proportional to the number of ions, while the transition to weaker solutions leads to the creation of multilayer hydration shells. This means that the number of perturbed water molecules, depending on the number of ions, increases according to a law different from linear. In accordance with the experimental data, the values of the absorption coefficients of aqueous solutions were determined in a wide range of concentrations for alkali metal sulfates. It is noted that alkali metal sulfates have physical properties that generalize the dynamics of dielectric constants depending on the concentration of the base substance. A monotonic increase in the values of the absorption coefficients of solutions with a decrease in the concentration of basic substances in the region of high dilutions was established with individual dynamics for each basic substance, reflecting the total hydration changes in salt solutions. Research has shown that the proposed method for measuring radio-thermal radiation fixes a significant difference in the values of the dielectric constants of aqueous solutions at high dilutions from their values for water.

Solvated Ions in Water

2016 ◽  
Author(s):  
Bruce C. Bunker ◽  
William H. Casey
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecules ◽  
Halide Ions ◽  
Bulk Fluid ◽  
Undergraduate Chemistry ◽  
Dissolved Species ◽  
Solvated Ions ◽  
Oxygen Anions ◽  
Chemical Attributes ◽  
Ionic Clathrate Hydrates

In most undergraduate chemistry classes, students are taught to consider reactions in which cations and anions dissolved in water are depicted as isolated ions. For example, the magnesium ion is depicted as Mg2+, or at best Mg2+(aq). For anions, these descriptions may be adequate (if not accurate). However, for cations, these abbreviations almost always fail to describe the critical chemical attributes of the dissolved species. A much more meaningful description of Mg2+ dissolved in water is [Mg(H2O)6]2+, because Mg2+ in water does not behave like a bare Mg2+ ion, nor do the waters coordinated to the Mg2+ behave anything like water molecules in the bulk fluid. In many respects, the [Mg(H2O)6]2+ ion acts like a dissolved molecular species. In this chapter, we discuss the simple solvation of anions and cations as a prelude to exploring more complex reactions of soluble oxide precursors called hydrolysis products. The two key classes of water–oxide reactions introduced here are acid–base and ligand exchange. First, consider how simple anions modify the structure and properties of water. As discussed in Chapter 3, water is a dynamic and highly fluxional “oxide” containing transient rings and clusters based on tetrahedral oxygen anions held together by linear hydrogen bonds. Simple halide ions can insert into this structure by occupying sites that would normally be occupied by other water molecules because they have radii (ranging from 0.13 to 0.22 nm in the series from F− to I−) that are comparable to that of the O2− ion (0.14 nm). Such substitution is clearly seen in the structures of ionic clathrate hydrates, where the anion can replace one and sometimes even two water molecules. Larger anions can also replace water molecules within clathrate hydrate cages. For example, carboxylate hydrate structures incorporate the carboxylate group within the water framework whereas the hydrophobic hydrocarbon “tails” occupy a cavity within the water framework, as in methane hydrate (see Chapter 3). Water molecules form hydrogen bonds to dissolved halide ions just as they can to other water molecules, as designated by OH−Y−.

A comparison of the mechanisms of hydrolysis of benzimidates, esters, and amides in sulfuric acid media

2005 ◽  
Vol 83 (9) ◽  
pp. 1391-1399 ◽  
Author(s):  
Robin A Cox
Keyword(s):  
Sulfuric Acid ◽  
Isotope Effects ◽  
Ester Hydrolysis ◽  
Water Molecules ◽  
Acid Media ◽  
Tetrahedral Intermediate ◽  
Amide Hydrolysis ◽  
Solvent Isotope ◽  
Reaction Media ◽  
Hydrolysis Of

The mechanisms given in textbooks for both ester and amide hydrolysis in acid media are in need of revision. To illustrate this, benzimidates were chosen as model compounds for oxygen protonated benzamides. In aqueous sulfuric acid media they hydrolyze either by a mechanism involving attack of two water molecules at the carbonyl carbon to give a neutral tetrahedral intermediate directly, as in ester hydrolysis, or by an SN2 attack of two water molecules at the alkyl group of the alkoxy oxygen to form the corresponding amide, or by both mechanisms, depending on the structure of the benzimidate. The major line of evidence leading to these conclusions is the behavior of the excess acidity plots resulting from the rate constants obtained for the hydrolyses as functions of acid concentration and temperature. The first of these mechanisms is in fact very similar to one found for the hydrolysis of benzamides, as inferred from: (1) similar excess acidity plot behaviour; and (2) the observed solvent isotope effects for amide hydrolysis, which are fully consistent with the involvement of two water molecules, but not with one or with three (or more). This mechanism starts out as essentially the same one as that found for ester hydrolysis under the same conditions. Differences arise because the neutral tetrahedral intermediate, formed directly as a result of the protonated substrate being attacked by two water molecules (not one), possesses an easily protonated nitrogen in the amide and benzimidate cases, explaining both the lack of 18O exchange observed for amide hydrolysis and the irreversibility of the reaction. Protonated tetrahedral intermediates are too unstable to exist in the reaction media; in fact, protonation of an sp3 hybridized oxygen to put a full positive charge on it is extremely difficult. (This means that individual protonated alcohol or ether species are unlikely to exist in these media either.) Thus, the reaction of the intermediate going to product or exchanged reactant is a general-acid-catalyzed process for esters. For amide hydrolysis, the situation is complicated by the fact that another, different, mechanism takes over in more strongly acidic media, according to the excess acidity plots. Some possibilities for this are given.Key words: esters, amides, benzimidates, hydrolysis, excess acidity, mechanism, acid media.

scholarly journals Crown ether alkali metal TCNQ complexes revisited – the impact of smaller cation complexes on their solid-state architecture and properties

CrystEngComm ◽  
2019 ◽  
Vol 21 (21) ◽  
pp. 3273-3279 ◽  
Author(s):  
Bingjia Yan ◽  
Peter N. Horton ◽  
Andrea E. Russell ◽  
Christopher J. Wedge ◽  
Simon C. Weston ◽  
...  
Keyword(s):  
Solid State ◽  
Crown Ether ◽  
Alkali Metal ◽  
Water Molecules ◽  
The Impact ◽  
Cation Complexes

Water molecules play a key structure-organising role in the crystallisation of 15-crown-5 complexes of lithium and sodium TCNQ in the presence of excess TCNQ0.

Isotope effects in nucleophilic substitution reactions. V. The mechanism of the decomposition of 1-phenylethyldimethylphenylammonium halides in chloroform

1986 ◽  
Vol 64 (6) ◽  
pp. 1206-1214 ◽  
Author(s):  
Helen Alma Joly ◽  
Kenneth Charles Westaway
Keyword(s):  
Ground State ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Steric Effects ◽  
Halide Ions ◽  
Substitution Reactions ◽  
Kinetic Isotope ◽  
Hydrogen Deuterium ◽  
Primary Substrate ◽  
Triple Ion

Secondary α and β hydrogen–deuterium kinetic isotope effects have been used together to show that the SN reaction between 1-phenylethyldimethylphenylammonium ion and bromide or iodide ion in chloroform occurs by way of an SN2 mechanism within a triple ion in spite of the fact that it reacts faster than the primary substrate, benzyldimethylphenylammonium bromide. The very loose transition state and steric effects in the ground state appear to be responsible for the unusually fast SN2 reactions between 1-phenylethyldimethylphenylammonium ion and halide ions in chloroform.

Tetrapyrrolic compounds as hosts for binding of halides and alkali metal cations

2009 ◽  
Vol 13 (11) ◽  
pp. 1148-1158 ◽  
Author(s):  
Mikalai M. Kruk ◽  
Aleksander S. Starukhin ◽  
Nugzar Zh. Mamardashvili ◽  
Galina M. Mamardashvili ◽  
Yulia B. Ivanova ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Pyridine Ring ◽  
Alkali Metal Cation ◽  
Metal Cations ◽  
Cation Binding ◽  
Halide Ions ◽  
Alkali Metal Cations ◽  
Cation Complexation ◽  
Iodide Ions ◽  
Binding Isotherms

In this paper the binding of halides and alkali metal cations with porphyrin hosts is reported. The halide ions are complexed with diprotonated porphyrin macrocycle with high affinity and stable complexes of 1:1 and 1:2 structures with halide ions are formed. Strong (up to 300 times) quenching of the porphyrin fluorescence has been found upon the titration of porphyrin solutions with iodide ions. It was established that both static quenching upon formation of the non-fluorescent complex and dynamic diffusion-controlled quenching took place. It is shown that the halide ions binding isotherms can be linearized with double-logarithmic plots. The alkali metal cations are trapped with mono-meso-arylporphyrins containing a conformationally mobile complexing polyether fragment on the benzene ring with a terminal pyridine ring. The alkali metal cation binding constant depends on the polyether chain length. The five-membered (n = 5) polyether chain provides very high binding selectivity for potassium over lithium or sodium. The potassium complexation constants 3.6 × 105 and 7.2 × 104 M-1 have been obtained for Zn 2+ complex and diprotonated porphyrin, respectively. For signaling of the alkali cation complexation, it is proposed to use the binding between the terminal pyridine ring with either the Lewis acidic site (chelated Zn 2+ ion) or the diprotonated macrocycle core ( H 4 P 2+) acting as salt bridging site.

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