The hydrolyses of some sterically crowded benzoate esters in sulfuric acid. The excess acidity method at different temperatures

1979 ◽  
Vol 57 (22) ◽  
pp. 2960-2966 ◽  
Author(s):  
Robin A. Cox ◽  
Malcolm F. Goldman ◽  
Keith Yates
Keyword(s):  
Sulfuric Acid ◽  
Activation Enthalpy ◽  
Sulfuric Acid Concentration ◽  
Hydrolysis Rate ◽  
Water Molecules ◽  
Steric Strain ◽  
Methyl Substitution ◽  
Different Temperatures ◽  
Acid Catalyzed ◽  
Aqueous Standard

The excess acidity method has been used to analyze the observed acid-catalyzed hydrolysis rate constants for methyl benzoate, methyl para-toluate, methyl ortho-toluate, and methyl 2,6-dimethylbenzoate, over a wide sulfuric acid concentration range, at several different temperatures. Enthalpies and entropies of activation in the aqueous standard state are reported, with slope parameters m≠ also given are the [Formula: see text] and m* values found for the protonation of these compounds. The mechanistic changeover from AAc-2 to AAc-1 hydrolysis occurs at lower acidity with increasing methyl substitution, mainly due to the decrease in activation enthalpy in the transition state for the AAc-1 process, caused by release of steric strain and increased mesomeric interaction. The AAc-2 hydrolysis involves two water molecules, and is energetically favourable and entropically unfavourable. The AAc-1 reaction is difficult energetically, but this is offset by the large positive activation entropies found.

The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile

1996 ◽  
Vol 74 (10) ◽  
pp. 1774-1778 ◽  
Author(s):  
Robin A. Cox
Keyword(s):  
Sulfuric Acid ◽  
Water Molecule ◽  
Rate Constants ◽  
Activation Parameters ◽  
Standard State ◽  
Aqueous Sulfuric Acid ◽  
Alkyl Groups ◽  
Different Temperatures ◽  
State Rate ◽  
Acid Catalyzed

In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82–85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m≠m* slopes also correlate with σ*, although the scatter is bad. Key words: N-nitro amines, excess acidity, bisulfate, nucleophiles, acid-catalyzed, kinetics.

Mechanistic studies in strong acids. VIII. Hydrolysis mechanisms for some thiobenzoic acids and esters in aqueous sulfuric acid, determined using the excess acidity method

1982 ◽  
Vol 60 (24) ◽  
pp. 3061-3070 ◽  
Author(s):  
Robin A. Cox ◽  
Keith Yates
Keyword(s):  
Sulfuric Acid ◽  
Proton Transfer ◽  
Strong Acid ◽  
Weak Acid ◽  
Medium Composition ◽  
Hydrolysis Rate ◽  
Water Molecules ◽  
Aqueous Sulfuric Acid ◽  
Ion Formation ◽  
Rate Determining Step

The excess acidity method has been applied to hydrolysis rate data, obtained as a function of medium composition, for four thiobenzoic acids, thioacetic acid, eight ethyl thiolbenzoates, and eight ethyl thionbenzoates in aqueous sulfuric acid. The mechanistic behaviour thus revealed has both similarities to and differences from that of a typical ester like ethyl benzoate, which gives benzoic acid by an A-2 reaction involving two water molecules in weak acid, and by A-1 acylium ion formation in strong acid. The thioacids follow this behaviour, except that the A-2 process involves three water molecules, and that the mechanistic changeover occurs in 60% rather than 80% acid. The A-2 process for the ethyl thiolbenzoates is slow; the major hydrolysis mechanism is acylium ion formation, not in an A-1 reaction but by a concerted A-SE2 process involving both proton transfer to sulfur and carbon–sulfur bond breaking. The major proton transfer agent is the undissociated sulfuric acid molecule. The thionbenzoate esters, in contrast, undergo very fast A-2 hydrolysis; so fast, in fact, that the initial protonation of sulfur is the rate-determining step in acids more dilute than about 62% w/w. It appears that proton transfer to sulfur is a comparatively slow process.

The hydrolyses of benzamides, methylbenzimidatium ions, and lactams in aqueous sulfuric acid. The excess acidity method in the determination of reaction mechanisms

1981 ◽  
Vol 59 (19) ◽  
pp. 2853-2863 ◽  
Author(s):  
Robin A. Cox ◽  
Keith Yates
Keyword(s):  
Sulfuric Acid ◽  
Water Molecule ◽  
Reaction Pathway ◽  
Sulfuric Acid Concentration ◽  
Strong Acid ◽  
Hydrolysis Rate ◽  
Reaction Conditions ◽  
Acid Media ◽  
Hydrolysis Of

The excess acidity method has been applied to hydrolysis rate data for a number of benzamides, methylbenzimidatium ions, and lactams, obtained as a function of sulfuric acid concentration and temperature. All of the substrates studied except β-propiolactam (8) and methyl-2,6-dimethylbenzimidatium ion (7) were found to follow the AOT2 mechanism at all acidities. The excess acidity method provided considerable mechanistic detail; in dilute acid the transition state contains O-protonated (or methylated) substrate and three water molecules (large negative ΔS≠), but in more concentrated solutions a one-water-molecule mechanism takes over (smaller negative ΔS≠). In strong acid bisulfate ion acts as the nucleophile (positive ΔS≠). N-protonated intermediates are not involved for "normal" substrates, being observed in this work only for 8, which follows the AND1 pathway. Observed differences between benzamide and methylbenzimidatium ion (4) hydrolyses are due to their differing activity coefficient behaviour, the mechanism being the same for both. The hydrolysis of 7 involves a one-water-molecule SN2 displacement at the O-methyl group. Comparison with 7 shows that this displacement is not likely to occur under the reaction conditions for 4; however, for the N-methyl and N,N-dimethyl derivatives studied it is probably an important reaction pathway. A comprehensive mechanistic framework for amide hydrolyses in strong acid media is given.

Study on Preparation of Titanium Dioxide from Low Iron and Rich Titanium Slag with Acid Hydrolysis Technical

2012 ◽  
Vol 554-556 ◽  
pp. 682-686
Author(s):  
Zhi Yong Hu
Keyword(s):  
Titanium Dioxide ◽  
Sulfuric Acid ◽  
Acid Hydrolysis ◽  
Process Parameters ◽  
Sulfuric Acid Concentration ◽  
Curing Temperature ◽  
Hydrolysis Rate ◽  
Optimum Process ◽  
Curing Time ◽  
Titanium Slag

Titanium dioxide is an important inorganic chemical product, and low iron and rich titanium slag can be made into titanium dioxide. In this paper, process parameters for preparing titanium dioxide were investigated. The results show that with the increase of sulfuric acid concentration, curing time and curing temperature, the rate of sulfuric acid hydrolysis rate will be improved, as well as charging temperature. According to the orthogonal test, the optimum process parameters condition of sulfuric acid is 95% sulfuric acid, 180°C reaction temperature, and 120min curing time.

Mechanistic variation in the reactions of substituted acetamides in aqueous sulfuric acid

1984 ◽  
Vol 62 (11) ◽  
pp. 2401-2414 ◽  
Author(s):  
Linda M. Druet ◽  
Keith Yates
Keyword(s):  
Sulfuric Acid ◽  
Water Molecules ◽  
Acid Solutions ◽  
Reaction Products ◽  
Aqueous Sulfuric Acid ◽  
Rate Determining Step ◽  
Wide Range ◽  
Acid Catalyzed ◽  
Catalyzed Reactions ◽  
Sulfuric Acid Solutions

The acid-catalyzed reactions of acetamide 1, N-tert-butylacetamide 2, and several p-substituted N-benzylacetamides (3 = H, 4 = CH3, 5 = OCH3, 6 = Cl, 7 = NO2) have been studied as a function of acidity and temperature over a wide range of aqueous sulfuric acid solutions (0–91%). Analysis of the reaction products and rate–acidity profiles revealed that four different mechanisms are operative over different acidity regions depending on the structure of the substrate. These are: two A-2 hydrolysis mechanisms with N-acyl fission of the substrate (with participation of one or several water molecules in the rate-determining step); A-1 hydrolysis with N-alkyl fission; and sulfonation, followed by hydrolysis. These conclusions are supported by three complementary and detailed kinetic treatments based on the hydration parameter, transition state activity coefficient, and excess acidity approaches. The acidity domains of each mechanism have been established for each substrate. The mechanistic conclusions are fully supported by the different values of ΔH‡ and ΔS‡ obtained in different regions of acidity.

An Expedient Approach to the Synthesis of Chloroacetic, Dichloroacetic and Acetic Acid Catalyzed by Sulfuric Acid in the Presence of Crown Ethers

2006 ◽  
Vol 3 (12) ◽  
pp. 940-942 ◽  
Author(s):  
Shahnaz Perveen ◽  
Tahira Sarfaraz ◽  
Khalid Khan ◽  
Wolfgang Voelter
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Crown Ethers ◽  
Acid Catalyzed

Simulation effect of SiO2 nanoparticles on the water molecules diffusion inside insulating oil at different temperatures

2021 ◽  
Vol 610 ◽  
pp. 125738
Author(s):  
Qinpan Qiu ◽  
Wenxin Tian ◽  
Lu Yang ◽  
Zhuyu Ding ◽  
Jingwen Zhang ◽  
...  
Keyword(s):  
Sio2 Nanoparticles ◽  
Water Molecules ◽  
Insulating Oil ◽  
Different Temperatures

scholarly journals Hydrothermal Pretreatment of Wheat Straw: Effects of Temperature and Acidity on Byproduct Formation and Inhibition of Enzymatic Hydrolysis and Ethanolic Fermentation

Agronomy ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 487
Author(s):  
Dimitrios Ilanidis ◽  
Stefan Stagge ◽  
Leif J. Jönsson ◽  
Carlos Martín
Keyword(s):  
Mass Spectrometry ◽  
Sulfuric Acid ◽  
Wheat Straw ◽  
High Performance ◽  
Enzymatic Saccharification ◽  
Hydrothermal Pretreatment ◽  
Gas Chromatography Mass Spectrometry ◽  
Enzymatic Digestibility ◽  
Acid Catalyzed ◽  
Pretreatment Conditions

Biochemical conversion of wheat straw was investigated using hydrothermal pretreatment, enzymatic saccharification, and microbial fermentation. Pretreatment conditions that were compared included autocatalyzed hydrothermal pretreatment at 160, 175, 190, and 205 °C and sulfuric-acid-catalyzed hydrothermal pretreatment at 160 and 190 °C. The effects of using different pretreatment conditions were investigated with regard to (i) chemical composition and enzymatic digestibility of pretreated solids, (ii) carbohydrate composition of pretreatment liquids, (iii) inhibitory byproducts in pretreatment liquids, (iv) furfural in condensates, and (v) fermentability using yeast. The methods used included two-step analytical acid hydrolysis combined with high-performance anion-exchange chromatography (HPAEC), HPLC, ultra-high performance liquid chromatography-electrospray ionization-triple quadrupole-mass spectrometry (UHPLC-ESI-QqQ-MS), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Lignin recoveries in the range of 108–119% for autocatalyzed hydrothermal pretreatment at 205 °C and sulfuric-acid-catalyzed hydrothermal pretreatment were attributed to pseudolignin formation. Xylose concentration in the pretreatment liquid increased with temperature up to 190 °C and then decreased. Enzymatic digestibility was correlated with the removal of hemicelluloses, which was almost quantitative for the autocatalyzed hydrothermal pretreatment at 205 °C. Except for the pretreatment liquid from the autocatalyzed hydrothermal pretreatment at 205 °C, the inhibitory effects on Saccharomyces cerevisiae yeast were low. The highest combined yield of glucose and xylose was achieved for autocatalyzed hydrothermal pretreatment at 190 °C and the subsequent enzymatic saccharification that resulted in approximately 480 kg/ton (dry weight) raw wheat straw.

scholarly journals Effective Recovery Process of Copper from Waste Printed Circuit Boards Utilizing Recycling of Leachate

JOM ◽  
2020 ◽  
Author(s):  
Joona Rajahalme ◽  
Siiri Perämäki ◽  
Roshan Budhathoki ◽  
Ari Väisänen
Keyword(s):  
Hydrogen Peroxide ◽  
Sulfuric Acid ◽  
Printed Circuit Boards ◽  
Sulfuric Acid Concentration ◽  
Recovery Process ◽  
Copper Recovery ◽  
Circuit Boards ◽  
Printed Circuit ◽  
Waste Printed Circuit Boards ◽  
Acid Consumption

AbstractThis study presents an optimized leaching and electrowinning process for the recovery of copper from waste printed circuit boards including studies of chemical consumption and recirculation of leachate. Optimization of leaching was performed using response surface methodology in diluted sulfuric acid and hydrogen peroxide media. Optimum leaching conditions for copper were found by using 3.6 mol L−1 sulfuric acid, 6 vol.% hydrogen peroxide, pulp density of 75 g L−1 with 186 min leaching time at 20°C resulting in complete leaching of copper followed by over 92% recovery and purity of 99.9% in the electrowinning. Study of chemical consumption showed total decomposition of hydrogen peroxide during leaching, while changes in sulfuric acid concentration were minor. During recirculation of the leachate with up to 5 cycles, copper recovery and product purity remained at high levels while acid consumption was reduced by 60%.

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