Elements Of Physical Chemistry Ed 2nd Samuel Glasstone. Glasstone. Topics: Physical chemistry. Collection DOWNLOAD OPTIONS. Physical Chemistry. by: Ph. D. D. Sc. Glasstone, phichamhokouda.ga: Ph. D. D. Sc. Glasstone, Samuel 1 Favorite. DOWNLOAD OPTIONS. Textbook of physical chemistry by Samuel Glasstone; 11 editions; First DAISY for print-disabled Download ebook for print-disabled (DAISY).
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Chemical kinetics. Surface phenomena. DOWNLOAD phichamhokouda.ga Text- book of Physical Chemistry Samuel Glasstone Come to Me Softly The Closer to. Textbook of Physical Chemistry. By Samuel Glasstone. Article Views are the COUNTER-compliant sum of full text article downloads since. 13 downloads 6 Views 2MB Size Sourcebook on Atomic Energy (Glasstone, Samuel). will find the Elements of Physical Chemistry (Glasstone, Samuel).
Zeroth law and absolute temperature scale. Experimental methods of studying kinetics of reactions- Principles of volumetric method [saponification of ester] and colorimetric method [iodination of acetone].
Effect of Temperature on reaction rates -Temperature coefficient. Arrhenius theory, concept of energy barrier. Bimolecular collision theory - [final equation given, no derivation].
Limitations of bimolecular collision theory. Transition state theory — qualitative approach. Steady state approximation, Lindamann theory - kinetics of unimolecular reactions. Fischer projection formulae; resolution using amines as resolving agents.
Chiral molecules that do not possess chiral centre — allene derivatives. Geometrical isomerism — E and Z nomenclature. Sigma bonds and bond rotation; conformational analysis of ethane and butane; relative stabilities of cycloalkanes; ring strain; origin of ring strain in cyclopropane and cyclobutane; angle strain.
Kalia; Vallabh Publications; Publishers; Organic Chemistry, T. Solomons, C.
Fryhle 9th Edition Willy India, Organic Chemistry, R. Morrison and R. Boyd, 6th Edition , Printice Hall, Organic Chemistry, Volume 1, I. Organic Chemistry, Volume 2, I. Laboratory safety procedures. Introduction to different types of glassware.
Handling and cleaning of apparatus. Methods of Separation and Purification Crystallization, distillation, fractional distillation, steam distillation, sublimation, determination of melting point and boiling point; chromatography — thin layer and column chromatography 3. Preparation of organic compounds: a Acetylation — preparation of acetanilide and aspirin b Nitration — preparation of m-dinitrobenzene and p-nitroacetanilide c Halogenation — preparation of p-bromoacetanilide and 2,4,6-tribromophenol d Oxidation — preparation of benzoic acid from benzaldehyde e Reduction — preparation of aniline from nitrobenzene f Hydrolysis — preparation of p-bromoaniline from p-bromoacetanilide 4.
Determination of equivalent weight of a carboxylic acid. Estimation of phenol. Estimation of nitro group. Reactivity, electrode potentials and reducing properties, reaction with water. Compounds — Oxides and peroxides-formation and reaction with water, basic character of oxides and hydroxides. Carbonates - thermal stability.
Reasons for anomalous behavior of Li and Be, diagonal relationship of Li and Mg. Group 13 Boron Family 3 Hours Electronic configuration, oxidation states, inert pair effect, metallic character, nature of bonds formed, basic character of oxides and hydroxides. Hydrides — classification of boron hydrides, diborane — preparation from BCl3, properties reactions with ammonia and Lewis acid properties and structure based on VBT.
Halides - comparison of Lewis acid character of boron trihalides. Group 14 Carbon Family 2 Hours Electronic configuration, oxidation states; inert pair effect, metallic character, nature of bonds formed, catenation, allotropic forms of carbon- diamond, graphite and fullerenes C 60 and their structures, carbon nanotubes brief mention without structural details.
Silicates — Classification, structures of ortho and pyrosilicates. Spontaneous and non-spontaneous processes, spontaneity and equilibrium. Driving force for spontaneous processes. Concept of entropy definition; Carnot cycle- derivation of efficiency based on entropy concept. Entropy change in adiabatic and isothermal reversible expansions of an ideal gas.
An Introduction To Electrochemistry
Change in entropy of an ideal gas with change in P, V and T derivation of equation. Entropy changes of an ideal gas for isothermal, isochoric and isobaric processes. Entropy of phase change. Entropy changes in the system and surroundings for reversible and irreversible expansions; Entropy as a criteria for spontaneity. Physical significance of entropy and relation between entropy and probability. Standard free energy change of a reaction. Free energy - criteria of spontaneity, variation of G with T and P.
Clausius—Clapeyron equation—derivation, application to liquid-vapour and solid-liquid equilibria. Vapour pressure curves of completely miscible liquids. Boiling point - composition curves of completely miscible liquids. Fractional distillation of binary liquid solutions. Effect of impurity on CST.
Nernst distribution law, application in the case of association and dissociation. Interfacial angles.
Symmetry in cubic systems- 23 elements of symmetry; Space lattice and unit cell. Bravais lattices, 7 crystal systems, 14 space lattices, law of rational indices.
Miller indices; Derivation of Braggs' equation, equation for inter-planar spacing only for cubic crystal system. X-Ray diffraction- Experimental determination of structure by rotating crystal method e.
NaCl and KCl. Nucleophilic substitution reaction, nucloephile, leaving group. SN2 reaction - kinetics, mechanism, energy profile, stereochemistry. SN1 reaction: stability of carbocations, kinetics, mechanism, energy profile, stereochemistry.
Nucleophilic substitution reactions in organic synthesis: Functional group interconversion using SN2 reactions. Acid catalysed dehydration of alcohols - mechanism. Reaction involving rearrangement of carbocations. Synthesis of alkynes by elimination of vicinal and geminal dihalides. The concept of active molecules, which was part of the original theory, was later discarded by Arrhenius as being unnecessary; he suggested that whenever a substance capable of yielding a conducting solution was dissolved in water, it dissociated spontaneously into ions, the extent of the dissociation being very considerable with salts and with strong acids and bases, especially in dilute solution.
Thus, a molecule of potassium chloride should, according to the theory of electrolytic dissociation, be split up into potassium and chloride ions in the following manner: If dissociation is complete, then each molecular particle of solid potassium chloride should give two particles in solution; the osmotic effect will thus approach twice the expected value, as has actually been found.
It is now known that the agreement referred to above, which convinced many scientists of the value of the Arrhenius theory, was to a great extent fortuitous; the conductance method for calculating the degree of dissociation is not applicable to salt solutions, and such solutions would, in any case, not be expected to obey the ideal gas law equation. Nevertheless, the theory of electrolytic dissociation, with certain modifications, is now universally accepted; it is believed that when a solute, capable of forming a conducting solution, is dissolved in a suitable solvent, it dissociates spontaneously into ions.
If the solute is a salt or a strong acid or base the extent of dissociation is very considerable, it being almost complete in many cases provided the solution is not too concentrated; substances of this kind, which are highly dissociated and which give good conducting solutions in water, are called strong electrolytes. Weak acids and weak bases, e.
These results are in harmony with modern developments of the ionic theory, as will be evident in later chapters. As is to be expected, it is impossible to classify all electrolytes as strong or weak, although this forms a convenient rough division which is satisfactory for most purposes.
Certain substances, e. It may be noted, too, that the nature of the solvent is often important; a particular compound may be a strong electrolyte, being dissociated to a large extent, in one solvent, but may be only feebly dissociated, and hence is a weak electrolyte, in another medium cf.
Evidence for the Ionic Theory. It is of interest, however, to review briefly some of the lines of evidence which support the ionic theory. Although exception may be taken to the quantitative treatment given by Arrhenius, the fact of the abnormal osmotic properties of electrolytic solutions still remains; the simplest explanation of the high values can be given by postulating dissociation into ions.
This, in conjunction with the ability of solutions to conduct the electric current, is one of the strongest arguments for the ionic theory.
Another powerful argument is based on the realization in recent years, as a result of X-ray diffraction studies, that the structural unit of solid salts is the ion rather than the molecule. That is to say, salts are actually ionized in the solid state, and it is only the restriction to movement in the crystal lattice that prevents solid salts from being good electrical conductors.
When fused or dissolved in a suitable solvent, the ions, which are already present, can move relatively easily under the influence of an applied E. The concept that salts consist of ions held together by forces of electrostatic attraction is also in harmony with modern views concerning the nature of valence. Many properties of electrolytic solutions are additive functions of the properties of the respective ions; this is at once evident from the fact that the chemical properties of a salt solution are those of its constituent ions.
For example, potassium chloride in solution has no chemical reactions which are characteristic of the compound itself, but only those of potassium and chloride ions. These properties are possessed equally by almost all potassium salts and all chlorides, respectively.
Similarly, the characteristic chemical properties of acids and alkalis, in aqueous solution, are those of hydrogen and hydroxyl ions, respectively. Certain physical properties of electrolytes are also additive in nature; the most outstanding example is the electrical conductance at infinite dilution. It will be seen in Chap. II that conductance values can be ascribed to all ions, and the appropriate conductance of any electrolyte is equal to the sum of the values for the individual ions.
The densities of electrolytic solutions have also been found to be additive functions of the properties of the constituent ions. The catalytic effects of various acids and bases, and of mixtures with their salts, can be accounted for by associating a definite catalytic coefficient with each type of ion; since undissociated molecules often have appreciable catalytic properties due allowance must be made for their contribution.
Certain thermal properties of electrolytes are in harmony with the theory of ionic dissociation; for example, the heat of neutralization of a strong acid by an equivalent amount of a strong base in dilute solution is about It is of interest to mention that the heat of the reaction between hydrogen and hydroxyl ions in aqueous solution has been calculated by an entirely independent method see p.
The heat of neutralization of a weak acid or a weak base is generally different from Influence of the Solvent on Dissociation. Experiments have been made on solutions of tetraisoamylammonium nitrate in a series of mixtures of water and dioxane see p. In the water-rich solvents the system behaves like a strong electrolyte, but in the solvents containing relatively large proportions of dioxane the properties are essentially those of a weak electrolyte.
In this case, and in analogous cases where the solute consists of units which are held together by bonds that are almost exclusively electrovalent in character, it is probable that the dielectric constant is the particular property of the solvent that influences the dissociation cf. II and III. The higher the dielectric constant of the medium, the smaller is the electrostatic attraction between the ions and hence the greater is the probability of their existence in the free state.
It should be noted, however, that there are many instances in which the dielectric constant of the solvent plays a secondary part: for example, hydrogen chloride dissolves in ethyl alcohol to form a solution which behaves as a strong electrolyte, but in nitrobenzene, having a dielectric constant differing little from that of alcohol, the solution is a weak electrolyte. As will be seen in Chap. IX the explanation of this difference lies in the ability of a molecule of ethyl alcohol to combine readily with a bare hydrogen ion, i.
Nitrobenzene, however, does not form such a combination to any great extent; hence the degree of dissociation of the acid is small and the solution of hydrogen chloride behaves as a weak electrolyte. The ability of oxygen compounds, such as ethers, ketones and even sugars, to accept a proton from a strongly acidic substance, thus forming an ion, e.
Another aspect of the formation of compounds and its influence on electrolytic dissociation is seen in connection with substituted ammonium salts of the type R3NHX; although they are strong electrolytes in hydroxylic solvents, e. If the solvent S is of such a nature, however, that its molecules tend to form strong hydrogen bonds, it can displace the X— ions, thus so that ionization of the salt is facilitated.
Hydroxylic solvents, in virtue of the type of oxygen atom which they contain, form hydrogen bonds more readily than do nitro-compounds, nitriles, etc. Salts of the type R4NX function as strong electrolytes in both groups of solvents, since the dielectric constants are relatively high, and the question of compound formation with the solvent is of secondary importance. The fact that salts of different types show relatively little difference of behavior in hydroxylic solvents has led to these substances being called levelling solvents.
On the other hand, solvents of the other group, e. The characteristic properties of the levelling solvents are due partly to their high dielectric constants and partly to their ability to act both as electron donors and acceptors, so that they are capable of forming compounds with either anions or cations.
The formation of a combination of some kind between the ion and a molecule of solvent, known as solvation, is an important factor in enhancing the dissociation of a given electrolyte. The solvated ions are relatively large and hence their distance of closest approach is very much greater than the bare unsolvated ions.
It will be seen in ; there is reason for believing that solvation is frequently electrostatic in character and is due to the orientation of solvent molecule dipoles about the ion. A solvent with a large dipole moment will thus tend to facilitate solvation and it will consequently increase the degree of dissociation. It was mentioned earlier in this chapter that acid amides and nitro-compounds form conducting solutions in liquid ammonia and hydrazine; the ionization in these cases is undoubtedly accompanied by, and is associated with, compound formation between solute and solvent.
The same is true of triphenylmethyl chloride which is a fair electrolytic conductor when dissolved in liquid sulfur dioxide; it also conducts to some extent in nitromethane, nitrobenzene and acetone solutions. In chloroform and benzene, however, there is no compound formation and no conductance. The amount of chemical decomposition produced by a current is proportional to the quantity of electricity passing through the electrolytic solution.
The amounts of different substances liberated by the same quantity of electricity are proportional to their chemical equivalent weights. The first law can be tested by passing a current of constant strength through a given electrolyte for various periods of time and determining the amounts of material deposited, on the cathode, for example; the weights should be proportional to the time in each case.
Further, the time may be kept constant and the current varied; in these experiments the quantity of deposit should be proportional to the current strength. The second law of electrolysis may be confirmed by passing the same quantity of electricity through a number of different solutions, e. These quantities are in the ratio of 1. Apart from small deviations, which can be readily explained by the difficulty of obtaining pure deposits on by similar analytical problems, there are a number of instances of more serious apparent exceptions to the laws of electrolysis.
The amount of sodium liberated in the electrolysis of a solution of the metal in liquid ammonia is less than would be expected. The quantities of metal deposited from solutions of lead or antimony in liquid ammonia containing sodium are in excess of those required by the laws of electrolysis; in these solutions the metals exist in the form of complexes and the ions are quite different from those present in aqueous solution. The applicability of the laws has been confirmed under extreme conditions: for example, Richards and Stull found that a given quantity of electricity deposited the same weight of silver, within 0.
The experimental results are quoted in Table II. Pressures up to atmospheres have no effect on the quantity of silver deposited from a solution of silver nitrate in water. The quantities of silver deposited in an ordinary silver coulometer in the various experiments are recorded, together with the amounts of silver gained by the cathode and lost by the anode, respectively, when solid silver iodide was used as the electrolyte.
The apparatus used for the latter purpose was at one time referred to as a voltameter, but the name coulometer, i. The most accurate determinations of the faraday have been made by means of the silver coulometer in which the amount of pure silver deposited from an aqueous solution of silver nitrate is measured.
The conditions for obtaining precise results have been given particularly by Rosa and Vinal : these are based on the necessity of insuring purity of the silver nitrate, of preventing particles of silver from the anode, often known as the anode slime, from falling on to the cathode, and of avoiding the inclusion of water and silver nitrate in the deposited silver.
The silver nitrate is purified by repeated crystallization from acidified solutions, followed by fusion. The purity of the salt is proved by the absence of the so-called volume effect, the weight of silver deposited by a given quantity of electricity being independent of the volume of liquid in the coulometer: this means that no extraneous impurities are included in the deposit. The solution of silver nitrate employed for the actual measurements should contain between 10 and 20 g.
The anode should be of pure silver with an area as large as the apparatus permits; the current density at the anode should not exceed 0. To prevent the anode slime from reaching the cathode, the former electrode A in Fig. The cathode is a platinum dish or cup C and its area should be such as to make the cathodic current density less than 0. The gain in weight gives the amount of silver deposited by the current; if the conditions described are employed, the impurities should not be more than 0.
Silver coulometers If the observations are to be used for the determination of the faraday, it is necessary to know exactly the quantity of electricity passed or the current strength, provided it is kept constant during the experiment.
In the work carried out at the National Physical Laboratory the absolute value of the current was determined by means of a magnetic balance, but at the Bureau of Standards the current strength was estimated from the known value of the applied E. According to the experiments of Smith, Mather and Lowry, one absolute coulomb deposits 1. The latter figure is identical with the one used for the definition of the international coulomb p. If the atomic weight of silver is taken as The accuracy of this law has been confirmed by many experiments with conductors of various types: it fails, apparently, for certain solutions when alternating currents of very high frequency are employed, or with very high voltages.
Since the international units were defined it has been found that they do not correspond exactly with those defined above in terms of the c. Silverstein, F. The purity of the salt is proved by the absence of the so-called volume effect, the weight of silver deposited by a given quantity of electricity being independent of the volume of liquid in the coulometer: this means that no extraneous impurities are included in the deposit. Nitrobenzene, however, does not form such a combination to any great extent; hence the degree of dissociation of the acid is small and the solution of hydrogen chloride behaves as a weak electrolyte.
It was necessary, therefore, to associate a negative charge with the electron, in order to be in harmony with the accepted convention concerning the direction of a current of electricity. In this case, and in analogous cases where the solute consists of units which are held together by bonds that are almost exclusively electrovalent in character, it is probable that the dielectric constant is the particular property of the solvent that influences the dissociation cf.
Textbook of Physical Chemistry
It was believed that when an acid, base or salt was dissolved in water a considerable portion, consisting of the so-called active molecules, was spontaneously split up, or dissociated, into positive and negative ions; it was suggested that these ions are free to move independently and are directed towards the appropriate electrodes under the influence of an electric field.
In chloroform and benzene, however, there is no compound formation and no conductance. Since the practical units are most frequently employed in electrochemistry, the most useful method of expressing the connection between the various units is to give the number of e.
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