This document summarizes a study that investigated the effect of increasing ethanol concentration on the rate of reaction between plasma albumin and formaldehyde. The rate constant was determined at various dielectric constants and temperatures by measuring absorption in ethanol-water mixtures containing plasma albumin and formaldehyde. The rate constant decreased with increasing ethanol concentration. Activation energy and other thermodynamic parameters also decreased with decreasing dielectric constant (increasing ethanol proportion). A linear relationship was observed between the log of the rate constant and the reciprocal of dielectric constant, indicating three mechanistic changes. The rate increased in water but decreased in ethanol, suggesting reaction rates were slowed by progressive ethanol addition. In conclusion, the reaction was second-order and its rate decreased with increasing ethanol concentration in accordance with
The Claisen rearrangement is a thermal rearrangement reaction discovered by Rainer Ludwig Claisen in which the allyl group of a phenolic allyl ether migrates ortho to the phenol group. Key characteristics of the Claisen rearrangement are the inversion of the migrating allyl carbon and the intramolecular, unimolecular nature of the reaction. The mechanism involves a cyclic transition state that allows for migration to the ortho position, or para if both ortho positions are blocked.
This document provides an overview of 10 common chemical oxidation reactions that can convert alcohols to aldehydes and ketones. It describes the reagents, reaction mechanisms, advantages/disadvantages, and examples for each reaction, including Jones oxidation, PCC oxidation, Swern oxidation, Dess-Martin periodinane oxidation, MnO2 oxidation, Babler oxidation, Corey-Kim oxidation, Parikh-Doering oxidation, Fetizon oxidation, and Oppenauer oxidation.
ELECTRICAL DOUBLE LAYER-TYPES-DYNAMICS OF ELECTRON TRANSFER-MARCUS THEORY-TUNNELING - BUTLER VOLMER EQUATIONS-TAFEL EQUATIONS-POLARIZATION AND OVERVOLTAGE-CORROSION AND PASSIVITY-POURBAIX AND EVAN DIAGRAM-POWER STORAGE-FUEL CELLS
The document discusses the lability and inertness of coordination complexes. It defines labile complexes as those where ligand exchange occurs rapidly, while inert complexes have slow ligand exchange. Lability is determined by factors like the metal ion size, charge, and d-electron configuration, not thermodynamic stability. Smaller or higher charged metal ions and complexes with less than 3 d-electrons tend to be more labile. The rate of ligand substitution depends on both the leaving and entering ligands. Steric effects and solvent also influence the rate. Complexes may undergo dissociative or associative substitution based on their structure.
The document discusses the nuclear Overhauser effect (NOE), which occurs when two protons are in close proximity within a molecule. Irradiating one proton perturbs its spin distribution and affects the relaxation of the other nearby proton. This causes the intensity of the other proton's signal to increase or decrease, indicating their proximity. The NOE provides information about molecular geometry without requiring coupling between nuclei and can reveal which protons are near each other in a structure.
Lithium aluminium hydride (LAH) is a strong reducing agent that is commonly used to reduce carbonyl groups, esters, amides, nitriles, epoxides, lactones, and haloalkanes/haloarenes. LAH is prepared through the reaction of lithium hydride with aluminum chloride. It is a white solid that reacts violently with water, producing hydrogen gas, so reactions must be performed under anhydrous conditions. The mechanism of LAH involves nucleophilic hydride attack on the carbonyl carbon to form an intermediate tetrahedral structure.
PTC IS THE PHASE TRANSFER CATALYSIS HERE TYPES OF PTC ARE DISCUSSED , THEORIES OF CATALYSIS AND MECHANISM OF PTC, ADVANTAGES OF PTC, APPLICATION OF PTC
The Claisen rearrangement is a thermal rearrangement reaction discovered by Rainer Ludwig Claisen in which the allyl group of a phenolic allyl ether migrates ortho to the phenol group. Key characteristics of the Claisen rearrangement are the inversion of the migrating allyl carbon and the intramolecular, unimolecular nature of the reaction. The mechanism involves a cyclic transition state that allows for migration to the ortho position, or para if both ortho positions are blocked.
This document provides an overview of 10 common chemical oxidation reactions that can convert alcohols to aldehydes and ketones. It describes the reagents, reaction mechanisms, advantages/disadvantages, and examples for each reaction, including Jones oxidation, PCC oxidation, Swern oxidation, Dess-Martin periodinane oxidation, MnO2 oxidation, Babler oxidation, Corey-Kim oxidation, Parikh-Doering oxidation, Fetizon oxidation, and Oppenauer oxidation.
ELECTRICAL DOUBLE LAYER-TYPES-DYNAMICS OF ELECTRON TRANSFER-MARCUS THEORY-TUNNELING - BUTLER VOLMER EQUATIONS-TAFEL EQUATIONS-POLARIZATION AND OVERVOLTAGE-CORROSION AND PASSIVITY-POURBAIX AND EVAN DIAGRAM-POWER STORAGE-FUEL CELLS
The document discusses the lability and inertness of coordination complexes. It defines labile complexes as those where ligand exchange occurs rapidly, while inert complexes have slow ligand exchange. Lability is determined by factors like the metal ion size, charge, and d-electron configuration, not thermodynamic stability. Smaller or higher charged metal ions and complexes with less than 3 d-electrons tend to be more labile. The rate of ligand substitution depends on both the leaving and entering ligands. Steric effects and solvent also influence the rate. Complexes may undergo dissociative or associative substitution based on their structure.
The document discusses the nuclear Overhauser effect (NOE), which occurs when two protons are in close proximity within a molecule. Irradiating one proton perturbs its spin distribution and affects the relaxation of the other nearby proton. This causes the intensity of the other proton's signal to increase or decrease, indicating their proximity. The NOE provides information about molecular geometry without requiring coupling between nuclei and can reveal which protons are near each other in a structure.
Lithium aluminium hydride (LAH) is a strong reducing agent that is commonly used to reduce carbonyl groups, esters, amides, nitriles, epoxides, lactones, and haloalkanes/haloarenes. LAH is prepared through the reaction of lithium hydride with aluminum chloride. It is a white solid that reacts violently with water, producing hydrogen gas, so reactions must be performed under anhydrous conditions. The mechanism of LAH involves nucleophilic hydride attack on the carbonyl carbon to form an intermediate tetrahedral structure.
PTC IS THE PHASE TRANSFER CATALYSIS HERE TYPES OF PTC ARE DISCUSSED , THEORIES OF CATALYSIS AND MECHANISM OF PTC, ADVANTAGES OF PTC, APPLICATION OF PTC
This document describes continuous wave (CW) NMR spectroscopy. It explains that CW-NMR uses a fixed magnetic field and varies the frequency coil current to achieve resonance signals. A typical CW spectrometer contains a sample tube spun between the poles of a powerful magnet. Radio frequency is broadcast into the sample while a receiver coil monitors the absorbed energy. By varying the magnetic field or radio frequency, an NMR spectrum is acquired showing signals from different proton types in the sample. While offering routine 1H NMR studies, CW spectroscopy has limitations such as low sensitivity, requirement for concentrated samples, and production of high noise.
Alkenes by absorption of light activated to higher energy singlet & triplet state and undergoes chemical reaction. These reactions are mainly:- 1. Cis - trans isomerization
2. Dimerization
3. Cycloaddition
This document provides an overview of homogeneous catalysis. It discusses several types of homogeneous catalytic reactions including hydrogenation, hydroformylation, hydrocyanation, and applications of chiral ligands. Key points made include that homogeneous catalysts are in the same phase as reactants, allowing them to accelerate chemical changes. Examples of industrial applications include hydrogenation in the food industry and hydroformylation in the production of aldehydes. Homogeneous catalysis also plays an important role in drug synthesis, with an example provided of the asymmetric hydrogenation used to produce the Parkinson's drug L-Dopa.
The Paternò-Büchi reaction involves the photochemical reaction between a carbonyl compound and an alkene to form an oxetane ring. This reaction was first reported in 1909 by Paternò and Chieffi. Several mechanisms are possible, including those involving a diradical intermediate or photoinduced electron transfer. The reaction shows regioselectivity, site selectivity, and stereoselectivity that depend on factors like the solvent, substituents on the carbonyl and alkene, and temperature. The Paternò-Büchi reaction has been used to synthesize biologically active oxetane-containing compounds and to construct more complex carbocyclic and heterocyclic ring systems.
This document summarizes types of oxidation reactions. It discusses 6 classes of dehydrogenation reactions: 1) aromatization of six-membered rings using catalysts, 2) reactions forming carbon-carbon double bonds, 3) dehydrogenation of alcohols to aldehydes and ketones, 4) oxidation of phenols and amines to quinones, 5) dehydrogenation of amines, and 6) oxidation of hydrazines, hydrazones, and hydroxylamines. Specific examples are provided for each class of reaction along with common reagents used to achieve the dehydrogenation or oxidation.
Racemisation is the process where a pure enantiomer is converted into a 50/50 mixture of both enantiomers, called a racemate. This can occur through various chemical reactions or physical changes that allow for inversion or interchange of chiral centres. Resolution is the separation of the enantiomers in a racemate. Several methods can be used to induce and monitor racemisation, such as changes in pH, temperature, catalysts, or conformational changes. Resolution techniques include forming diastereomeric salts, molecular complexes, or exploiting kinetic or thermodynamic differences in reactions.
This document provides an overview of the application of phase rule to a three component system of acetic acid, chloroform, and water. It defines key terms like phases, components, and degrees of freedom. It explains Gibbs phase rule and how it applies to a three component system. Specifically, it discusses how the water-acetic acid-chloroform system can be represented on a triangular phase diagram, with acetic acid enhancing the miscibility of water and chloroform. The document outlines how the system transitions from two heterogeneous phases to a single homogeneous phase as the amount of acetic acid is increased.
The document discusses several carbon-carbon bond forming reactions:
1. Aldol condensation allows aldehydes and ketones to undergo self-condensation in the presence of a base to form β-hydroxy carbonyl compounds.
2. The Perkin reaction uses an acid anhydride to form α,β-unsaturated aromatic acids from aromatic aldehydes.
3. The Wittig reaction converts a carbonyl group to an alkene using a phosphonium ylide.
The document introduces the Heck reaction, which is a coupling reaction where a metal catalyst aids in coupling two hydrocarbon fragments. Specifically, the Heck reaction involves converting a terminal alkene to an internal alkene. Richard Heck, Ei-ichi Negishi, and Akira Suzuki were jointly awarded the Nobel Prize in 2010 for their work developing palladium-catalyzed C-C cross coupling reactions, including the Heck reaction. The mechanism of the Heck reaction involves oxidative addition, insertion, β-H elimination, and reductive elimination steps.
This document provides an overview of reduction reactions in organic chemistry. It discusses various types of reduction reactions including catalytic hydrogenation, hydride transfer reactions using reagents like LiAlH4 and NaBH4, dissolving metal reductions, and others. Specific metal hydride reductions using boron and aluminum reagents like sodium borohydride, sodium cyanoborohydride, lithium aluminum hydride, and diisobutylaluminum hydride are explained in detail including their mechanisms and selectivity. Diimide reduction is also briefly covered. The document concludes with a bibliography of reference books on organic reaction mechanisms.
This document discusses radiometric titration, which uses a radioactive titrant. It describes the key elements of titration including the standard solution, analyte, equivalence point, and end point. There are four main types of radiometric titration: precipitation-based, complexation-based, redox-based, and those performed in non-aqueous media. Radiometric titration has applications in investigating co-precipitation in nuclear chemistry and determining the specific activity of radioactive preparations.
Pericyclic reactions involve the formation and breaking of bonds in a concerted cyclic transition state. They can be classified as cycloadditions, electrocyclic reactions, sigmatropic rearrangements, cheletropic reactions, or group transfers. Examples of important pericyclic reactions discussed include the Diels-Alder reaction, 1,3-dipolar cycloadditions, Claisen rearrangement, and electrocyclic ring openings and closings. These reactions are useful in synthesis and occur in biological systems.
This document summarizes the rearrangement of benzilic acid from benzil. It introduces benzilic acid and notes that it can be prepared through rearrangement of the 1,2-α-diketone benzil. The document then outlines the preparation of benzil, the rearrangement mechanism involving nucleophilic addition and migration, and properties of the resulting benzilic acid including its white crystalline structure and solubility in alcohols. Hazards of benzilic acid are also mentioned, noting it is very hazardous if in contact with skin or eyes or if ingested or inhaled, and that it is chemically stable under recommended storage conditions.
The document discusses pericyclic reactions and the Woodward-Hoffmann rules for predicting their stereochemistry. It begins by defining pericyclic reactions as concerted reactions where bonds are formed or broken in a cyclic transition state. It then provides examples of different types of pericyclic reactions, including electrocyclizations, cycloadditions, and sigmatropic rearrangements. The Woodward-Hoffmann theory is explained, showing how it can be used to predict whether a reaction will proceed with antarafacial conrotation or suprafacial disrotation based on whether the reaction is thermally or photochemically induced. Specific examples like cyclobutene formation and the Diels-Alder reaction are analyzed in
This document provides an overview of pericyclic reactions, including:
1. It classifies pericyclic reactions into four main categories: electrocyclic reactions, cycloaddition reactions, sigmatropic rearrangements, and ene reactions.
2. It discusses the Woodward-Hoffmann rules for determining the stereochemistry of pericyclic reactions under thermal and photochemical conditions.
3. It provides examples of specific pericyclic reactions, such as the Diels-Alder reaction and sigmatropic shifts, analyzing the frontier molecular orbitals involved.
This document discusses theories of unimolecular reaction kinetics, including the Lindemann-Christiansen theory, Hinshelwood theory, RRK theory, and RRKM theory. It notes limitations of earlier theories in explaining experimental data. The RRKM theory, developed by Marcus in 1951-1952, redefined the RRK treatment and addressed prior limitations. RRKM theory is now widely used to interpret thermal and photochemical reactions and allows calculating reaction rates from known vibrational frequencies of molecules.
The document discusses the Linear Free Energy Relationship known as the Hammett Equation. It describes how the Hammett Equation can be used to investigate organic reaction mechanisms by studying the effects of substituents on reaction rates. The key aspects are:
1) The Hammett Equation relates the logarithm of reaction rates or equilibrium constants to substituent constants (σ) using the reaction constant (ρ).
2) σ values describe electronic properties of substituents, with electron-withdrawing groups having positive σ and electron-donating groups having negative σ.
3) ρ indicates how sensitive a reaction is to substituents, relating the electronic demand of the reaction transition state. Its sign and magnitude provide insight into
Solvent plays a crucial role in the reaction. So we should smartly work with solvent. This presentation tries to summarizes the role as well as the effects of the solvent on the different reactions.
Art is a creative expression that stimulates the senses or imagination according to Felicity Hampel. Picasso believed that every child is an artist but growing up can stop that creativity. Aristotle defined art as anything requiring a maker and not being able to create itself.
This document describes continuous wave (CW) NMR spectroscopy. It explains that CW-NMR uses a fixed magnetic field and varies the frequency coil current to achieve resonance signals. A typical CW spectrometer contains a sample tube spun between the poles of a powerful magnet. Radio frequency is broadcast into the sample while a receiver coil monitors the absorbed energy. By varying the magnetic field or radio frequency, an NMR spectrum is acquired showing signals from different proton types in the sample. While offering routine 1H NMR studies, CW spectroscopy has limitations such as low sensitivity, requirement for concentrated samples, and production of high noise.
Alkenes by absorption of light activated to higher energy singlet & triplet state and undergoes chemical reaction. These reactions are mainly:- 1. Cis - trans isomerization
2. Dimerization
3. Cycloaddition
This document provides an overview of homogeneous catalysis. It discusses several types of homogeneous catalytic reactions including hydrogenation, hydroformylation, hydrocyanation, and applications of chiral ligands. Key points made include that homogeneous catalysts are in the same phase as reactants, allowing them to accelerate chemical changes. Examples of industrial applications include hydrogenation in the food industry and hydroformylation in the production of aldehydes. Homogeneous catalysis also plays an important role in drug synthesis, with an example provided of the asymmetric hydrogenation used to produce the Parkinson's drug L-Dopa.
The Paternò-Büchi reaction involves the photochemical reaction between a carbonyl compound and an alkene to form an oxetane ring. This reaction was first reported in 1909 by Paternò and Chieffi. Several mechanisms are possible, including those involving a diradical intermediate or photoinduced electron transfer. The reaction shows regioselectivity, site selectivity, and stereoselectivity that depend on factors like the solvent, substituents on the carbonyl and alkene, and temperature. The Paternò-Büchi reaction has been used to synthesize biologically active oxetane-containing compounds and to construct more complex carbocyclic and heterocyclic ring systems.
This document summarizes types of oxidation reactions. It discusses 6 classes of dehydrogenation reactions: 1) aromatization of six-membered rings using catalysts, 2) reactions forming carbon-carbon double bonds, 3) dehydrogenation of alcohols to aldehydes and ketones, 4) oxidation of phenols and amines to quinones, 5) dehydrogenation of amines, and 6) oxidation of hydrazines, hydrazones, and hydroxylamines. Specific examples are provided for each class of reaction along with common reagents used to achieve the dehydrogenation or oxidation.
Racemisation is the process where a pure enantiomer is converted into a 50/50 mixture of both enantiomers, called a racemate. This can occur through various chemical reactions or physical changes that allow for inversion or interchange of chiral centres. Resolution is the separation of the enantiomers in a racemate. Several methods can be used to induce and monitor racemisation, such as changes in pH, temperature, catalysts, or conformational changes. Resolution techniques include forming diastereomeric salts, molecular complexes, or exploiting kinetic or thermodynamic differences in reactions.
This document provides an overview of the application of phase rule to a three component system of acetic acid, chloroform, and water. It defines key terms like phases, components, and degrees of freedom. It explains Gibbs phase rule and how it applies to a three component system. Specifically, it discusses how the water-acetic acid-chloroform system can be represented on a triangular phase diagram, with acetic acid enhancing the miscibility of water and chloroform. The document outlines how the system transitions from two heterogeneous phases to a single homogeneous phase as the amount of acetic acid is increased.
The document discusses several carbon-carbon bond forming reactions:
1. Aldol condensation allows aldehydes and ketones to undergo self-condensation in the presence of a base to form β-hydroxy carbonyl compounds.
2. The Perkin reaction uses an acid anhydride to form α,β-unsaturated aromatic acids from aromatic aldehydes.
3. The Wittig reaction converts a carbonyl group to an alkene using a phosphonium ylide.
The document introduces the Heck reaction, which is a coupling reaction where a metal catalyst aids in coupling two hydrocarbon fragments. Specifically, the Heck reaction involves converting a terminal alkene to an internal alkene. Richard Heck, Ei-ichi Negishi, and Akira Suzuki were jointly awarded the Nobel Prize in 2010 for their work developing palladium-catalyzed C-C cross coupling reactions, including the Heck reaction. The mechanism of the Heck reaction involves oxidative addition, insertion, β-H elimination, and reductive elimination steps.
This document provides an overview of reduction reactions in organic chemistry. It discusses various types of reduction reactions including catalytic hydrogenation, hydride transfer reactions using reagents like LiAlH4 and NaBH4, dissolving metal reductions, and others. Specific metal hydride reductions using boron and aluminum reagents like sodium borohydride, sodium cyanoborohydride, lithium aluminum hydride, and diisobutylaluminum hydride are explained in detail including their mechanisms and selectivity. Diimide reduction is also briefly covered. The document concludes with a bibliography of reference books on organic reaction mechanisms.
This document discusses radiometric titration, which uses a radioactive titrant. It describes the key elements of titration including the standard solution, analyte, equivalence point, and end point. There are four main types of radiometric titration: precipitation-based, complexation-based, redox-based, and those performed in non-aqueous media. Radiometric titration has applications in investigating co-precipitation in nuclear chemistry and determining the specific activity of radioactive preparations.
Pericyclic reactions involve the formation and breaking of bonds in a concerted cyclic transition state. They can be classified as cycloadditions, electrocyclic reactions, sigmatropic rearrangements, cheletropic reactions, or group transfers. Examples of important pericyclic reactions discussed include the Diels-Alder reaction, 1,3-dipolar cycloadditions, Claisen rearrangement, and electrocyclic ring openings and closings. These reactions are useful in synthesis and occur in biological systems.
This document summarizes the rearrangement of benzilic acid from benzil. It introduces benzilic acid and notes that it can be prepared through rearrangement of the 1,2-α-diketone benzil. The document then outlines the preparation of benzil, the rearrangement mechanism involving nucleophilic addition and migration, and properties of the resulting benzilic acid including its white crystalline structure and solubility in alcohols. Hazards of benzilic acid are also mentioned, noting it is very hazardous if in contact with skin or eyes or if ingested or inhaled, and that it is chemically stable under recommended storage conditions.
The document discusses pericyclic reactions and the Woodward-Hoffmann rules for predicting their stereochemistry. It begins by defining pericyclic reactions as concerted reactions where bonds are formed or broken in a cyclic transition state. It then provides examples of different types of pericyclic reactions, including electrocyclizations, cycloadditions, and sigmatropic rearrangements. The Woodward-Hoffmann theory is explained, showing how it can be used to predict whether a reaction will proceed with antarafacial conrotation or suprafacial disrotation based on whether the reaction is thermally or photochemically induced. Specific examples like cyclobutene formation and the Diels-Alder reaction are analyzed in
This document provides an overview of pericyclic reactions, including:
1. It classifies pericyclic reactions into four main categories: electrocyclic reactions, cycloaddition reactions, sigmatropic rearrangements, and ene reactions.
2. It discusses the Woodward-Hoffmann rules for determining the stereochemistry of pericyclic reactions under thermal and photochemical conditions.
3. It provides examples of specific pericyclic reactions, such as the Diels-Alder reaction and sigmatropic shifts, analyzing the frontier molecular orbitals involved.
This document discusses theories of unimolecular reaction kinetics, including the Lindemann-Christiansen theory, Hinshelwood theory, RRK theory, and RRKM theory. It notes limitations of earlier theories in explaining experimental data. The RRKM theory, developed by Marcus in 1951-1952, redefined the RRK treatment and addressed prior limitations. RRKM theory is now widely used to interpret thermal and photochemical reactions and allows calculating reaction rates from known vibrational frequencies of molecules.
The document discusses the Linear Free Energy Relationship known as the Hammett Equation. It describes how the Hammett Equation can be used to investigate organic reaction mechanisms by studying the effects of substituents on reaction rates. The key aspects are:
1) The Hammett Equation relates the logarithm of reaction rates or equilibrium constants to substituent constants (σ) using the reaction constant (ρ).
2) σ values describe electronic properties of substituents, with electron-withdrawing groups having positive σ and electron-donating groups having negative σ.
3) ρ indicates how sensitive a reaction is to substituents, relating the electronic demand of the reaction transition state. Its sign and magnitude provide insight into
Solvent plays a crucial role in the reaction. So we should smartly work with solvent. This presentation tries to summarizes the role as well as the effects of the solvent on the different reactions.
Art is a creative expression that stimulates the senses or imagination according to Felicity Hampel. Picasso believed that every child is an artist but growing up can stop that creativity. Aristotle defined art as anything requiring a maker and not being able to create itself.
The Influence of Solvent on the Solvolysis of Ethyl Cinnamate in Water Aceton...IJEACS
The kinetic of alkaline hydrolysis of Ethyl Cinnamate was investigated at different percentage of aqua-organic solvent mixture with Acetone (30 to 70% v/v) over the temperature range of 20o C to 40 o C. The specific rate constant was found to be decreased with increasing proportion of solvent (Acetone) at all the temperature range. The Iso-composition Activation energy (EC) was also evaluated which decreases with solvent composition in (water-Acetone) system. The number of water molecule associated with the activated complex is found to be increase (0.7003to 0.786) in water-Acetone system. The Thermodynamic Activation Parameter such as Enthalpy of Activation (H*), Entropy of Activation (S*) and Gibb's free energy of activation (G*) were also calculated
Solvents and volatile substances can cause intoxication when inhaled and abused. They work by being absorbed quickly through the lungs into the bloodstream and passing rapidly to the brain. Common volatile substances that are abused include gases like butane, aerosols, glues, and other organic solvents found in products like paint thinners. While initial use may cause euphoria, solvent abuse can have serious health risks and has resulted in thousands of deaths in the UK since 1971.
The document discusses the effect of immersion solvent and time on photosensitization of TiO2 with protoporphyrin IX (PPIX). It finds that the adsorption and aggregation of sensitizing dyes on TiO2 is strongly dependent on the immersion solvent. Using a good solvent can prevent dye aggregation, allowing all dye molecules to act as photovoltaic active species. In contrast, a poor solvent may cause dye aggregation on the surface and reduce device performance. The maximum efficiency is achieved by optimizing the immersion time to control dye aggregation. Characterization with UV-Vis, FT-IR and fluorescence spectroscopy can provide insights into dye adsorption and charge transfer kinetics.
This document discusses various types of organic reactions including ionic reactions, radical reactions, and nucleophilic substitution reactions. It provides details on:
1) The mechanisms of SN1 and SN2 reactions including rate laws, stereochemistry, substrate structure effects, and effects of nucleophiles, leaving groups, and solvents. SN1 reactions proceed through a carbocation intermediate and follow first-order kinetics while SN2 reactions are bimolecular.
2) Substrate structures that favor SN1 or SN2 reactions. Tertiary substrates favor SN1 while primary and secondary favor SN2. Allylic and benzylic compounds are more reactive in both SN1 and SN2 reactions.
3)
A solvent can be any substance, that turns into a solution by dissolving a solid, liquid, or gaseous solute. The solvent is usually a liquid, but can also be a solid or gas.
Factors affecting drug stability include temperature, pH, buffering species, ionic strength, and dielectric constant. Temperature is an important factor because most reactions proceed faster at higher temperatures according to the Arrhenius equation. pH also affects stability, with most drugs being stable between pH 4-8, as hydrogen and hydroxide ions can catalyze degradation reactions. Buffering species like hydrogen and hydroxide ions participate in formation and breakdown of reaction intermediates. Ionic strength influences rates of reactions between ionic species, while dielectric constant affects rates of ion-dipole and ion-ion reactions. These physicochemical factors must be considered in stability testing and shelf life determination of pharmaceutical products.
This document discusses reaction kinetics, including the order of reactions, factors that influence reaction rates, and complexation. It defines zero, first, second, and pseudo-first order reactions based on their rate equations. Reaction rates can be influenced by physical factors like temperature, pH, and light exposure as well as chemical factors like acid-base catalysis and oxidation-reduction. Complexation refers to chemical reactions where a metal ion binds to a ligand containing an unshared pair of electrons.
This document discusses various factors that affect the degradation of drugs, including physical degradation, chemical degradation, temperature, solvent, ionic strength, dielectric constant, and catalysis. It provides examples of specific drugs that undergo different types of degradation, such as hydrolysis, oxidation, and photolysis. Equations are presented that describe the effects of temperature, solvent, ionic strength, and dielectric constant on reaction rates. Methods to prevent or minimize different degradation pathways like the use of antioxidants, chelating agents, buffers, and oxygen-free storage are also summarized.
Solvation can be defined as any stabilizing interaction of a solute (or solute moiety) and the solvent. These interactions can be weak, purely electrostatic, as is the case with non-polar solutes and solvents, or more significant, involving the interactions between dipole moments or between dipoles and formal charges.
Contributed by: Anton S. Klimenko (Undergraduate), Department of Chemistry, The University of Utah, 2016
Mechanism of the Reaction of Plasma Albumin with Formaldehyde in Ethanol - Wa...IOSR Journals
The Spectrophotometric determination of the acid dissociation/ionisation constant (pKa) of plasma albumin-formaldehyde adduct in both water solution and Ethanol solutions was carried out in this study. The pKa values obtained in both media were used to establish the Bronsted-linear type constants from plots of pKa against logarithm of second order rate constants obtained at varying pHs in the study. The result of the pKa values obtained in both water solution and ethanol-water mixtures were found to be in the range of 5.0 - 8.0. This pointed to the fact that only lysine residue with pKa value 8.3 that might have possibly reacted with formaldehyde in this reaction of all the known amino acid residues in plasma albumin. The corresponding Brønsted-type plots proportionality constants (β) for the reaction in water and ethanol-water mixtures were found to be β = 0.059 and 0.0057 respectively. The reaction mechanisms that have low values for proportionality constants α or β are considered to have a transition state closely resembling the reactant with little proton transfer (Cox et al, 1988). Thus, one would suggest that the cross-linking of formaldehyde with plasma albumin in water and ethanol-water mixtures proceeds through little proton transfer
Chemical Kinetics and Catalysis -Absolute Reaction Rate Theory in thermodynam...RamiahValliappan2
Absolute Reaction Rate Theory in thermodynamic terms – Significance of
entropy and volume of activation. Ionic reactions – primary and secondary salt
effects - Acid-base catalysis – Bronsted relations, catalytic coefficients and their
determination. Enzyme catalysis - Michaelis-Menten equation – Heterogeneous
catalysis-Langmuir-Hinshelwood and Eley- Rideal mechanisms General features of
fast reactions – Study of fast reactions by flow methods.
KINETICS OF STABILITY , ACCELERATED STABILITY STUDY, AND ICH STABILITY GUIDEL...Akhila Anil
CHEMICAL KINETICS
ORDER OF REACTION
DETERMINATION OF ORDER
SALIENT FEATURES OF ACCELERATED DRUG STABILITY
STABILITY METHOD
LIMITATIONS OF ACCELERATED DRUG STABILITY
ICH GUIDELINES ON STABILITY
Hsslive-xii-chem-slide-ch-4. Chemical Kinetics.pdfjayanethaji
1. Chemical kinetics deals with the study of rates of chemical reactions, factors influencing reaction rates, and reaction mechanisms.
2. Instantaneous reactions occur very fast, while slow reactions can take days to years to complete. Examples of slow reactions include rusting of iron and weathering of rocks.
3. The rate of a reaction is defined as the change in concentration of reactants or products per unit time. Rate laws describe how reaction rates depend on reactant concentrations.
The document discusses cheletropic reactions, which involve the concerted formation or breaking of two sigma bonds at a single atom. It provides examples of reactions involving sulfur dioxide and carbene additions to alkenes to form cyclopropanes. It also discusses theoretical analyses, kinetics, thermodynamics, solvent effects, and orbital symmetry considerations for these types of pericyclic reactions.
Kinetic Study of Esterification of Acetic Acid with n- butanol and isobutanol...Hugo Balderrama
The document summarizes a study on the kinetics of esterification reactions between acetic acid and n-butanol or isobutanol catalyzed by ion exchange resin. The effects of temperature, catalyst loading, and initial molar ratios on reaction rates were examined. Activation energies for the reactions were determined to be 28.45 kJ/mol for n-butanol and 23.29 kJ/mol for isobutanol. The study found reaction rates increased with higher temperatures, catalyst loadings, and molar ratios of alcohol to acid.
This opinion article aims to highlight the use of the Word Association technique (WA) as a food safety tool, as evidenced in the article by J.M. Latorres and coauthors.
Liquid-Liquid Equilibria of Nitrobenzene-Inorganic Acid Systems at 298.15 KReddysuresh Kolavali
Liquid-liquid equilibria of nitrobenzene-sulfuric acid-water and nitrobenzene-nitric acid-water systems were experimentally determined at 298.15 K. The NRTL and UNIQUAC models were used to correlate the experimental data with good fits and low root-mean-square deviations. Both acid solubility in the organic phase and nitrobenzene solubility in the aqueous phase increased with higher acid concentrations in the mixtures.
Enzymes use several catalytic mechanisms to lower the free energy of transition states and greatly increase reaction rates, including acid-base catalysis, covalent catalysis, metal ion catalysis, and bringing substrates into close proximity and proper orientation. Acid-base catalysis involves proton transfer from catalytic amino acid side chains. Covalent catalysis transiently forms covalent bonds between enzyme and substrate. Metal ion catalysis uses transition metals to orient substrates, mediate redox reactions, or stabilize charges. Proximity and orientation align substrates for reaction, while catalysis by approximation brings two substrates together for reaction.
Application of Statistical and mathematical equations in Chemistry Part 3Awad Albalwi
Application of Statistical and mathematical equations in Chemistry
Part 3
reaction rate
equilibrium constant
The common ion effect
Activity and Activity Coefficients
The Diverse Ion Effect Theory
Unit-5 Physical Pharmacy-II Drug stability.pptxssp183
The document discusses drug stability and International Conference on Harmonization (ICH) guidelines for stability testing. It provides details on:
1) Chemical kinetics and reaction order (zero, first, second, pseudo-first order) and how they impact degradation rate calculations.
2) Factors that influence drug stability like temperature, solvent, ionic strength, dielectric constant, and acid/base catalysts.
3) Common degradation pathways like hydrolysis, oxidation, photolysis and methods to prevent or minimize degradation through each pathway.
4) ICH guidelines divide stability testing guidelines into quality, safety, efficacy and multidisciplinary categories to ensure drug quality and efficacy globally.
Concept of rate of reaction.
Factors effecting rate of reaction.
Concept of order of reaction.
Methods for the determination of order of reaction.
Pharmaceutical importance and applications of rate and order of reaction.
Unit –II : Chemical Dynamics Potential energy surfaces, Kinetic isotopic effe...RamiahValliappan2
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The effect of dielectric constant on the kinetics of reaction between plasma albumin and formaldehyde in ethanol water mixtures
1. Chemistry and Materials Research www.iiste.org
ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online)
Vol.3 No.9, 2013
137
The Effect of Dielectric Constant On The Kinetics of Reaction
Between Plasma Albumin And Formaldehyde In Ethanol- Water
Mixtures.
*1
Ugye T .J , 2
Uzairu, A; 2
Idris , S.O; 3
Kwanashie,H.O.
1
Department of Chemical Sciences, Federal University,P.M.B 1020 Wukari
2
Department of Chemistry, Ahmadu Bello University, Zaria.
3
Department of Pharmacology and Therapeutics, Ahmadu Bello University, Zaria.
*Corresponding Author:phone:+2348069519202; EmaiL:torugye2007@yahoo.co.uk
Abstract
This study determined the effect of increased concentration of ethanol solution on the rate of the reaction
between plasma albumin and formaldehyde. It was design to investigate the kinetics of reaction between plasma
albumin and low concentrations of formaldehyde under pseudo-first order conditions of formaldehyde. The
reaction was studied at constant conditions at various dielectric constants and temperatures of 1%, 5%,
15%,20% and 200
C 250
C, 300
C and 370
C respectively. The rate constant as a function of different permittivity
in ethanol-water mixtures was determined at constant conditions. The dielectric constant of the reaction
medium was altered by the addition of the varying amounts of ethanol – water mixtures (1- 25% v/v) in a
cuvette and the absorption of 0.51 x10-4
mol dm-3
plasma albumin and 0.27 x10-1
formaldehyde- plasma
mixtures at 235 nm were measured. The values of dielectric constants for different aqueous ethanol- mixtures
were taken from literature. The values of rate constants of the reaction of between plasma albumin and
formaldehyde were found to decreased with the increase in the concentration of ethanol and the reaction was a
second order or bimolecular . The Activation energy and the thermodynamic parameters (Gibbs free energy,
enthalpy and entropy changes of the reaction) decreased with decrease in dielectric constant of the medium,
that is with increase in the proportion of the ethanol component in the solvent mixtures. The dependence of
lnk2 vs. reciprocal dielectric constant (1/D ) of this reaction was found be linear with three linear portions
indicating three zones, that is three mechanistic changes. Also the correlations between lnk2 and the mole
fractions of water and ethanol ( χH2O and χEtOH) have shown that there was an increase in rate of the studied
reaction in water but a decrease in rate in ethanol mole fraction. This leads us to suggest that the reaction rates
were slowed by progressive addition of ethanol . A steady decrease in rate constant with decrease in dielectric
constant values was observed with a statistically significant p-value = 0.0013 on a two tailed correlation analysis
at 95% confidence assurance.
Key Words; dielectric constant, kinetics , plasma albumin, formaldehyde , ethanol- water mixtures.
Introduction
The dielectric constant of a solvent roughly provides a measure of the solvent's polarity. A dielectric constant
below 15 is usually considered non-polar. Basically, the dielectric constant can be thought of as the solvent's
ability to reduce the internal charge of the solvent. The hydrogen atom in a polar protic solvent is reported to
be highly positively charged, and it can interact with the anionic nucleophile which would negatively affect an
bimolecular nucleophilic substitution reaction(SN2
), but it does not affect an unimolecular nucleophilic
substitution (SN1
) reaction because the nucleophile is not a part of the rate-determining[1]. Hence it found
that the higher the dielectric constant the more polar the substance and in the case of SN1 reactions, the faster the
rate. Polar protic solvents are known to actually speed up the rate of the unimolecular substitution reaction
because the large dipole moment of the solvent helps to stabilize the transition state. The highly positive and
highly negative parts interact with the substrate to lower the energy of the transition state. Since the carbocation
is unstable, anything that can stabilize this even a little will speed up the reaction [1].
Solvents used in substitution reactions were found to inherently determine the nucleophilicity of the
nucleophile. This fact has become increasingly more apparent as more reactions are performed in the gas phase.
As such, solvent conditions significantly affect the performance of a reaction with certain solvent conditions
favouring one reaction mechanism over another. For SN1 reactions the solvent's ability to stabilize the
intermediate carbocation is of direct importance to its viability as a suitable solvent. The ability of polar solvents
to increase the rate of SN1 reactions is as a result of the polar solvent's solvating the reactant intermediate
species, i.e., the carbocation, thereby decreasing the intermediate energy relative to the starting material [2].
Huges [3] however found that the case for SN2 reactions is quite different, as the lack of solvation on the
nucleophile increases the rate of an SN2 reaction. In either case (SN
1
or SN
2
), the ability to either stabilize the
transition state (SN
1
) or destabilize the reactant starting material (SN
2
) acts to decrease the ∆G‡
of activation and
2. Chemistry and Materials Research www.iiste.org
ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online)
Vol.3 No.9, 2013
138
thereby increase the rate of the reaction. This relationship is according to the equation ∆G = -RT ln K (Gibb's
free energy). The rate equation for SN
2
reactions are bimolecular being first order in nucleophile and first order
in reagent. The determining factor when both SN
2
and SN
1
reaction mechanisms are viable is the strength of the
nucleophile. Nuclephilicity and basicity are linked and the more nucleophilic a molecule becomes the greater is
the nucleophile’s basicity. This increase in bacisity causes problems for SN
2
reaction mechanisms when the
solvent of choice is protic. Protic solvents react with strong nucleophiles with good basic character in an
acid/base fashion, thus decreasing or removing the nucleophilic nature of the nucleophile. It is important to note
that solvent effects as well as steric effects both affect the relative reaction rates; however, for demonstration of
principle for solvent polarity on SN2 reaction rates, steric effects may be neglected. There are two major factors
affecting the reactivity of a specific amino acid side chain toward a reagent that under ideal conditions reacts
with it. These are; effects on the pK of the reacting group (which affects its nucleophilicity), and steric effects.
The reaction between plasma albumin and formaldehyde an aprotic solvent in water ethanol solutions is
essential essential since formaldehyde will undergo addition reactions with most protic solvents and is a good
hydrogen bond acceptor [4] . A study by [5] found that Apolar solvents did not solubilise denatured proteins, but
low solubilizing powers were observed for polar, aprotic solvents. Heat denaturation was observed to result in
the formation of large intermolecular aggregates,m which, for ovalbumin and lysozyme, were formed by
intermolecular S-S bonds, but for bovine serum albumin involved intermolecular iso peptide bond This study
therefore investigated the effect of increase in the concentration of ethanol in a solution on the rate of the
reaction partly denatured plasma albumin and formaldehyde The study was also aimed at ascertaining the
molecularity this reaction from the results and to shade more light on this important reaction that is often
found to occur in alcoholic systems.
Materials and Method
The reaction was studied at constant conditions at various dielectric constants and temperatures of 1%, 5%,
15%, 20% and 200
C 250
C, 300
C and 370
C respectively. The rate constant as a function of different permittivity
in ethanol-water mixtures was determined at constant conditions. The dielectric constant of the reaction
medium was altered by the addition of the varying amounts of ethanol – water mixtures (1- 25% v/v) in a
cuvette and the absorption of 0.51 x10-4
mol dm-3
plasma albumin and 0.27 x10-1
formaldehyde- plasma
mixtures at 235 nm were measured. Rate was measured in (1% to 25% v/v) Ethanol- water mixtures. The values
of dielectric constants for different aqueous Ethanol- mixtures were taken from literature [6, 7]. Triplicate values
were taken in each case to obtain the pseudo-first and second order rate kinetics from a plot of ln (At - A∞) versus
time. The Erying plots, that logk2/T vs 1/T for different dielectric constant were plotted and the thermodynamic
parameters were calculated from the relation ln(k2 / T) = - ∆H҂
/RT + ∆S҂
/ R + 23.8 while the activation energy
was calculated by using the expression Ea = ∆H҂
+ RT [8,9]. (The values of the thermodynamic parameters
energy were determined as a function of dielectric constant of medium the results recorded. Also the values of
the second order rate constant logk2 were plotted against reciprocal dielectric constant to obtain the relation of
the change in dielectric constant and the rate of the reaction between plasma Albumin and Formaldehyde.
Results and Discussions
Tables 1-11 and Fig. 1 - 8 provide the data for rate constant of plasma albumin and formaldehyde
reaction at various compositions of ethanol in water solution. The values of rate constants were found to
decreased with the increase in the concentration of ethanol, this deviation from the Bronsted theory is in
accordance to the literature [9]. The reason for such behaviour is reported to be due to the greater influence of
ionic orientation for regulating the reaction rate. The probability of ideal orientation is found to be maximum at
extreme dilution and higher value of dielectric constant. The probability of formation of a more polar transition
state is favourable in a medium of high dielectric constant [9].
The values of energy of activation other thermodynamic parameters as a function of dielectric constant of
medium at varying temperatures are as given in Table 10. The activation energies and the other
thermodynamic parameters were found to be effected by solvent medium. All the parameters, activation
energy the other thermodynamic parameters (Gibbs free energy, enthalpy and entropy changes of the reaction)
decreased with decrease in dielectric constant of the medium, that is with increase in the proportion of the
ethanol component in the solvent mixtures. This behaviour is reported to be in accordance with the idea of
solvation of activated complex [10].
Also a report by [11] showed that using the logarithm of a reaction rate constant versus the reciprocal of the
dielectric constant one may determine whether the reaction mechanism is changed, modifying the dielectric
constant equation of the binary mixtures due to the changes in its composition. According the authors a range of
3. Chemistry and Materials Research www.iiste.org
ISSN 2224- 3224 (Print) ISSN 2225- 0956 (Online)
Vol.3 No.9, 2013
139
solvent composition in which the equations of logarithm of a reaction rate constant versus the reciprocal of the
dielectric constant are linear is called “zone”. A solvent composition in which a zone finishes and another zone
initiates is called “mechanism change point.” The dependence of lnk2 vs. reciprocal dielectric constant (1/D ) of
this reaction was found be linear as shown in Fig.5 with three linear portions indicating three zones, three
mechanistic changes.
The correlations between lnk2 and the mole fractions of water and ethanol ( χH2O and χEtOH ) have shown
that there was an increase in rate of the studied reaction in water but a decrease in rate in ethanol mole
fraction. This leads us to suggest that the reaction rates were slowed by progressive addition of Ethanol as
presented in Fig 6 and 7. A steady decrease in rate constant with decrease in dielectric constant values was
observed with a statistically significant p-value of 1.000 on a two tailed correlation analysis at 95% confidence
assurance and result was also presented as in Table 11 and Fig. 8.
Conclusion
The values of rate constants were found to decreased with the increase in the concentration of ethanol, this
deviation from the Bronsted theory is in accordance to the literature [10] .The reason for such behaviour is
reported to be due to the greater influence of ionic orientation for regulating the reaction rate. The probability of
ideal orientation is found to be maximum at extreme dilution and higher value of dielectric constant. The
probability of formation of a more polar transition state is favourable in a medium of high dielectric constant
[10]. The activation energies and the other thermodynamic parameters were found to be effected by solvent
medium. Activation energy the other thermodynamic parameters (Gibbs free energy, enthalpy and entropy
changes of the reaction) decreased with decrease in dielectric constant of the medium, that is with increase in
the proportion of the ethanol component in the solvent mixtures. This behaviour is reported to be in
accordance with the idea of solvation of activated complex [10] . The dependence of lnk2 vs. reciprocal dielectric
constant (1/D ) of this reaction was found be linear as shown in Fig. 5 with three linear portions indicating
three zones, three mechanistic changes.
The correlations between lnk2 and the mole fractions of water and ethanol ( χH2O and χEtOH ) have shown
that there was an increase in rate of the studied reaction in water but a decrease in rate in ethanol mole
fraction. This leads us to suggest that the reaction rates were slowed by progressive addition of ethanol. A
steady decrease in rate constant with decrease in dielectric constant values was observed with a statistically
significant p-value = 0.0013 on a two tailed correlation analysis at 95% confidence assurance.his study therefore
investigated the effect of increase in the concentration of ethanol in a solution on the rate of the reaction
partly denatured plasma albumin and formaldehyde The study also found that the studied reaction second
order reaction in ethanol-water systems.
Competing Interests:
The Authors wish to declare that there are no conflicts of interest associated with this work.
Authors' Contributions:
Professor Uzairu,A; H.O Kwanashie, H.O, and Idris , S. O conceived and designed the research as well as
carefully proof read the the manuscript. Ugye, T. J performed the analysis and prepared the draft manuscript.
Acknowledgement
This work was not supported by any donor agent, however we wish to appreciate the contributions of Prof.
Kehinde Okonjo of the Department of Chemistry, Convenant University, Ota - Nigeria , Dr. S.G Yiase and Mr
S.O Adejo as well as the technical staff of ABU Zaria and the Benue State University , Makurdi for their
assistance and in facilitating the conduct of the bench Chemistry of this study in their various laboratories.
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Table 1 Experimental results of the rate constants of reaction of plasma Albumin and formaldehyde at
varying dielectric constants and temperature in [Ethanol-water] mixtures and T= 20 - 370
C at constant
conditions, λmax = 235 nm, pH= 7±3
%Ethanol Rate constant k2 mol-1
s-1
at different temperatures o
C
20 25 30 37
1 2.93 2.74 2.67 2.63
5 2.44 2.41 2.33 1.96
15 2.89 2.74 2.48 2.22
20 2.81 2.67 2.59 2.22
Table 2 Experimental Results of Pseudo - first order and second order rate constants at 2.7 x 10-1
mol/dm3
HCHO of formaldehyde with Plasma albumin reaction at different temperatures and Ethanol-
water mixtures
Ionic strength = 0.5 1%Ethanol –water mixture
K kobs k2 1/T x10-3
logk2 k2/T log (k2/T)
293 0.079 2.93 3.41 0.467 0.010 -2.000
298 0.074 2.74 3.36 0.438 0.0092 -2.036
303 0.072 2.67 3.30 0.427 0.0088 -2.056
310 0.071 2.63 3.23 0.420 0.0085 -2.071
Figure 1 Erying Plot of logk2/T versus 1/T at 1%ethanol-water mixture
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Table 3 Thermodynamic Parameters ( ∆G, ∆H≠
and ∆S≠
) and Ea for the Reaction of formaldehyde
with plasma Albumin in 1%(Ethanol water) mixture at different temperatures(200
C,250
C,300
C and
370
C.
[HCHO] moldm-3
Ea (kJmol-1
) ∆G≠
(kJmol-1
) ∆H≠
(kJmol-1
) ∆S≠
(Jmol-1
K-1
)
2.7 x10-1
1.89 66.880 -0.951. -225.351
Table 4 Experimental Results of Pseudo - first order and second order rate constants at 2.7 x 10-1
mol/dm3
HCHO of formaldehyde with Plasma albumin reaction at different temperatures and
5%Ethanol-water mixture
Ionic strength = 0.5 5.0 %Ethanol –water mixture
K kobs k2 1/T x10-3
logk2 k2/T log (k2/T)
293 0.066 2.44 3.41 0.387 0.0083 -2.081
298 0.065 2.41 3.36 0.382 0.008 -2.097
303 0.063 2.33 3.30 0.367 0.0077 -2.114
310 0.053 1.96 3.23 0.292 0.0063 -2.201
Figure 2 Erying Plot of lnk2/T versus 1/T at 5%ethanol-water mixture
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Table 5 Thermodynamic Parameters ( ∆G, ∆H≠
and ∆S≠
) and Ea for the Reaction of formaldehyde
with plasma Albumin in 5%(Ethanol water) mixture at different temperatures(200
C,250
C,300
C and
370
C
[HCHO] moldm-3
Ea (kJmol-1
) ∆G≠
(kJmol-1
) ∆H≠
(kJmol-1
) ∆S≠
(Jmol-1
K-1
)
2.7 x10-1
0.891 59.232 -1.612. -202.139
Table 6 Experimental Results of Pseudo - first order and second order rate constants at 2.7 x 10-1
mol/dm3
HCHO of formaldehyde with Plasma albumin reaction at different temperatures and
15%Ethanol-water mixture
Ionic strength = 0.5 15%Ethanol –water mixture
K kobs k2 1/Tx10-3
logk2 k2/T log (k2/T)
293 0.078 2.89 3.41 0.461 0.010 -2.000
298 0.074 2.74 3.36 0.438 0.009 -2.046
303 0.067 2.48 3.30 0.394 0.008 -2.097
310 0.060 2.22 3.23 0.346 0.007 -2.155
Figure 3 Erying Plot of lnk2/T versus 1/T at 15 %ethanol-water mixture
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Table 7 Thermodynamic Parameters ( ∆G, ∆H≠
and ∆S≠
) and Ea for the Reaction of formaldehyde
with plasma Albumin in 15%(Ethanol water) mixture at different temperatures(200
C,250
C,300
C and
370
C
[HCHO] moldm-3
Ea (kJmol-1
) ∆G≠
(kJmol-1
) ∆H≠
(kJmol-1
) ∆S≠
(Jmol-1
K-1
)
2.7 x10-1
0.355 59.301 -2.148 -202.802
Table 8 Experimental Results of Pseudo - first order and second order rate constants at
2.7 x 10-1
mol/dm3
HCHO of formaldehyde with Plasma albumin reaction at different temperatures and
20%Ethanol-water mixture
Ionic strength = 0.5 moldm-3
20 %Ethanol –water mixture
K kobs k2 1/Tx10-3
logk2 k2/T log (k2/T)
293 0.076 2.81 3.41 0.449 0.010 -2.000
298 0.072 2.67 3.36 0.427 0.009 -2.046
303 0.070 2.59 3.30 0.413 0.008 -2.097
310 0.060 2.22 3.23 0.346 0.007 -2.155
Figure 4 Erying Plot of lnk2/T versus 1/T at 20%ethanol-water mixture
Table 9 Thermodynamic Parameters ( ∆G, ∆H≠
and ∆S≠
) and Ea for the Reaction of formaldehyde
with plasma Albumin in 20%(Ethanol water) mixture at different temperatures(200
C,250
C,300
C and
370
C
[HCHO] moldm-3
∆Ea (kJmol-1) ∆G≠
(kJmol-1
) ∆H≠
(kJmol-1
) ∆S≠
(Jmol-1
K-1
)
2.7 x10-1
0.355 59.301 -2.148 -202.802
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Table 10 Thermodynamics and other Parameters for Reaction in Various ethanol–Water Media. Temp.
= 20 - 37o
C ,ionic strength = 0.5
Solventcompost % Ea
(k Jmol-1
)
∆G≠
(kJmol-1
) ∆H≠
(kJmol-1
) ∆S≠
(Jmol-1
K-1
)
1 1.290 66.880 -0.951 -225.351
5 0.891 59.232 -1.612 -202.139
15 0.355 59.301 -2.148 -202.802
20 0.355 59.301 -2.148 -202.802
Mean 0.723 61.18 -1.715 -208.27
Figure 5 plot lnk2 vs, 1/D showing the effect of change in dielectric constants change on the rate constant on
the reaction of plasma albumin with formaldehyde in ethanol-water mixtures.
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Figure 6 plot of lnk2 vs. mole fractions of water
Figure. 7 plot of lnk2 vs. mole fractions of ethanol –water mixture
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Table 11 Results of two tailed correlation analysis for k2 values versus ethanol -mixtures at 95% level
of assurance.
Best-fit values
Slope -0.02810 ± 0.003482
Y-intercept when X=0.0 3.023 ± 0.05273
X-intercept when Y=0.0 107.5
1/slope -35.58
95% Confidence Intervals
Slope -0.03777 to -0.01844
Y-intercept when X=0.0 2.876 to 3.169
X-intercept when Y=0.0 83.14 to 157.4
Goodness of Fit
r² 0.9421
Sy.x 0.07080
Is slope significantly non-zero?
F 65.14
DFn, DFd 1.000, 4.000
P value 0.0013
Deviation from zero? Significant
Data
Number of X values 6
Maximum number of Y replicates 1
Total number of values 6
Number of missing values 0
Runs test
Points above line 4
Points below line 2
Number of runs 5
P value (runs test) 1.0000
Deviation from linearity Not Significant
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0 10 20 30
0
20
40
60
80
100
k2
dielectric const
eth-H20
k2
Figure 8 Correlational analysis chart of k2 values versus dielectric constants at different ethanol-water
mixtures.
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