Alkylammonium Ions: Chemical Shifts and Interactions with Solvent in Aqueous Acid Solutions

1971 ◽  
Vol 49 (13) ◽  
pp. 2364-2366 ◽  
Author(s):  
J. T. Edward
Keyword(s):  
Sulfuric Acid ◽  
Chemical Shifts ◽  
Acid Solutions ◽  
Aqueous Acid ◽  
Tentative Explanation ◽  
The Difference

The difference between the chemical shifts of the α and β hydrogens of the mono-, di-, tri-, and tetra-ethylammonium ions changes as the concentration of the solvent sulfuric acid is increased from 0 to 94%. A tentative explanation based on hydration of the ions is presented.

Studies of azo and azoxy dyestuffs. Part 18. Kinetics and mechanism of the hydrolysis of 3- and 4-(p′-methoxyphenylazo)pyridines in aqueous sulfuric acid media

1986 ◽  
Vol 64 (11) ◽  
pp. 2115-2126 ◽  
Author(s):  
Erwin Buncel ◽  
Ikenna Onyido
Keyword(s):  
Sulfuric Acid ◽  
Transition States ◽  
Activation Parameters ◽  
Nucleophilic Attack ◽  
Acid Solutions ◽  
Acid Media ◽  
Charge Delocalization ◽  
Leaving Group ◽  
The Difference ◽  
Hydrolysis Of

The kinetics of hydrolysis of 4-(p′-methoxyphenylazo)pyridine, 1, and its 3-isomer, 2, have been studied in moderately concentrated sulfuric acid media at 25 °C. In all the acid solutions investigated, 1 reacted faster than 2; rate differences between the two compounds varied from ca. 1000-fold in the dilute region of acidity to ca. 250-fold in the more concentrated acid solutions. The observed first-order rate constants, kψ, for both substrates exhibit a maximum, at ca. 42% H2SO4 and 47% H2SO4 for 1 and 2 respectively. Activation parameters have also been determined. The pKa values for the second protonation equilibria of 1 and 2 have been evaluated and structures of the diprotonated species are discussed. Hydrolysis is shown to occur from the diprotonated substrates and two main mechanisms are operative. The first is an A-2 type mechanism, which involves rate-limiting attack of H2O on the aryl carbon center giving delocalized transition states and intermediates in which the pyridinium and azonium functions are involved in charge delocalization. Subsequent transfer of a proton and detachment of the leaving group are fast processes. In the second A-SE2 type mechanism, nucleophilic attack and transfer of the proton are fast steps preceding the slow general acid catalyzed separation of the leaving group. The difference in reactivity of the two compounds is attributed to differences in extent of charge delocalization in the transition states of the reactions: for 1 both the pyridinium and protonated azonium functions are involved whereas for 2 only the azonium function participates in charge delocalization.

Medium effects on tetraalkylammonium ions in aqueous acid solutions

1976 ◽  
Vol 54 (9) ◽  
pp. 1439-1444 ◽  
Author(s):  
Tomasz A. Modro ◽  
William F. Reynolds ◽  
Keith Yates
Keyword(s):  
Aqueous Solutions ◽  
Chemical Shifts ◽  
Ionic Species ◽  
Acid Solutions ◽  
Medium Effects ◽  
Tetraalkylammonium Ions ◽  
Aqueous Acid ◽  
Low Field ◽  
Cation Hydration ◽  
Strong Acids

Medium effects upon 1H and 13C chemical shifts have been determined for some tetraalkylammonium ions in 0–10 M aqueous solutions of H2SO4, HClO4, and H3PO4. The observed effects are very weak in magnitude, thus justifying the choice of tetraalkylammonium ions as reference standards for studies of ionic species in aqueous solutions of strong acids. The trends in the observed low-field shifts are interpreted in terms of changes in cation hydration and in hydrogen bonding between alkyl hydrogens and acid anions.

Acid-catalyzed enolization of acetophenone: catalysis by bisulfate ion in sulfuric acid solutions

1986 ◽  
Vol 64 (6) ◽  
pp. 1224-1227 ◽  
Author(s):  
J. R. Keeffe ◽  
A. J. Kresge ◽  
J. Toullec
Keyword(s):  
Aqueous Solution ◽  
Sulfuric Acid ◽  
Acidity Constant ◽  
Acidity Function ◽  
Acid Solutions ◽  
Dilute Aqueous Solution ◽  
Acid Catalyzed ◽  
The Difference ◽  
Carbon Acid ◽  
Sulfuric Acid Solutions

Rates of acid-catalyzed enolization of acetophenone in dilute aqueous solution, measured under conditions where the solvated proton is the only acidic species present, give a hydrogen ion catalytic coefficient, [Formula: see text], that is 35% smaller than the value obtained by X acidity function extrapolation of measurements made in moderately concentrated sulfuric acid solutions. The difference may be attributed to catalysis by bisulfate ion in the sulfuric acid solutions; this is supported by direct measurement of the bisulfate ion catalytic coefficient in dilute sulfuric acid. This revised value of [Formula: see text] leads to new, but only slightly different, values of the keto–enol equilibrium constant for acetophenone in aqueous solution, pKE = 7.96 ± 0.04, the acidity constant for acetophenone ionizing as a carbon acid, [Formula: see text] and the encounter-controlled rate constant for the reaction of acetophenone enol with molecular bromine, k = (3.2 ± 0.4) × 109 M−1 s−1.

Photocatalytic Splitting of Liquid Water by n-TiO2 Suspension

1981 ◽  
Vol 36 (8) ◽  
pp. 876-879 ◽  
Author(s):  
Waltraud Vonach ◽  
Nikola Getoff
Keyword(s):  
Grain Size ◽  
Sulfuric Acid ◽  
Electron Donor ◽  
Liquid Water ◽  
Reaction Mechanisms ◽  
Acid Solutions ◽  
Aqueous Acid ◽  
Probable Reaction ◽  
Evolution Of Oxygen

Abstract By illumination (λ>300 nm) of a suspension of n-TiO2 (grain size ≦0.06 mm, 3 to 15 mg/ml) in aqueous acid solutions, containing 10-3 mol · dm-3 Ce4+ -ions an enhanced evolution of oxygen is observed. Its yield is dependent on the amount of TiO2 in the suspension and on the temperature. Using n-TiO2 suspended in diluted sulfuric acid, hydrogen and oxygen were produced in a ratio of about 2: 1. In both systems n-TiO2 is acting as an efficient electron donor. For the explanation of the processes probable reaction mechanisms are proposed.

Protection features of chromium-nickel steel in sulfuric acid solutions by triazole derivative

2019 ◽  
pp. 15-21
Author(s):  
Ya.G. Avdeev ◽  
◽  
Yu.B. Makarychev ◽  
D.S. Kuznetsov ◽  
L.P. Kazanskii ◽  
...  
Keyword(s):  
Sulfuric Acid ◽  
Nickel Steel ◽  
Acid Solutions ◽  
Triazole Derivative ◽  
Sulfuric Acid Solutions

Synthesis and characterization of a series of 1-methyl-4-[2-aryl-1-diazenyl]piperazines and a series of ethyl 4-[2-aryl-1-diazenyl]-1-piperazinecarboxylates

2004 ◽  
Vol 82 (8) ◽  
pp. 1294-1303 ◽  
Author(s):  
Vanessa Renée Little ◽  
Keith Vaughan
Keyword(s):  
Free Energy ◽  
Chemical Shifts ◽  
Linear Free Energy Relationship ◽  
Piperazine Ring ◽  
Linear Free Energy ◽  
In Series ◽  
Methylene Groups ◽  
Diazonium Coupling ◽  
The Difference

1-Methylpiperazine was coupled with a series of diazonium salts to afford the 1-methyl-4-[2-aryl-1-diazenyl]piperazines (2), a new series of triazenes, which have been characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, and elemental analysis. Assignment of the chemical shifts to specific protons and carbons in the piperazine ring was facilitated by comparison with the chemical shifts in the model compounds piperazine and 1-methylpiperazine and by a HETCOR experiment with the p-tolyl derivative (2i). A DEPT experiment with 1-methylpiperazine (6) was necessary to distinguish the methyl and methylene groups in 6, and a HETCOR spectrum of 6 enabled the correlation of proton and carbon chemical shifts. Line broadening of the signals from the ring methylene protons is attributed to restricted rotation around the N2-N3 bond of the triazene moiety in 2. The second series of triazenes, the ethyl 4-[2-phenyl-1-diazenyl]-1-piperazinecarboxylates (3), have been prepared by similar diazonium coupling to ethyl 1-piperazinecarboxylate and were similarly characterized. The chemical shifts of the piperazine ring protons are much closer together in series 3 than in series 2, resulting in distortion of the multiplets for these methylenes. It was noticed that the difference between these chemical shifts in 3 exhibited a linear free energy relationship with the Hammett substituent constants for the substituents in the aryl ring. Key words: triazene, piperazine, diazonium coupling, NMR, HETCOR, linear free energy relationship.

Electrochemistry of Gold in Aqueous Sulfuric Acid Solutions under Neural Stimulation Conditions

2005 ◽  
Vol 152 (7) ◽  
pp. E212 ◽  
Author(s):  
Daniel R. Merrill ◽  
Ionel C. Stefan ◽  
Daniel A. Scherson ◽  
J. Thomas Mortimer
Keyword(s):  
Sulfuric Acid ◽  
Neural Stimulation ◽  
Acid Solutions ◽  
Aqueous Sulfuric Acid ◽  
Sulfuric Acid Solutions
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