AN INTRODUCTION. TO. ELECTROCHEMISTRY. BY. SAMUEL GLASSTONE, D. Sc, PH.D. Consultant, United Stales Atomic Energy Commission. Download An Introduction To Electrochemistry (PDF P) Download free online book chm pdf. Author(s): Glasstone, Samuel. s Pages. Download / View. Introduction to Electrochemistry. By Samuel Glasstone. View: PDF | PDF w/ Links. Related Content By H. S. Taylor and Samuel Glasstone. The Journal of.

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Strategic Bombing Survey in Hiroshima and Nagasaki. It enabled activists to calculate enormous numbers of potential casualties by taking a tiny risk and multiplying it by the population of the earth.

As an enduring consequence, the perceived risks of radiation are far out of proportion to actual risks, causing tremendous damage to the American nuclear industry. Efforts to save lives were not only futile, but unethical: Any suggestion that nuclear war could be survivable increased its likelihood and was thus tantamount to warmongering, PSR spokesmen warned.

Later U.

Army assignments included the U. In , he received his MSc from the University of Virginia. He later calculated the neutron induced activity in the soil, and predicted the hazard from the rainout of radioactivity from air bursts in thunderstorms.

Glasstone used Dolan's decay curves in the and later editions of The Effects of Nuclear Weapons. After retiring from the U. In , Dolan compiled the famous U.

Robert Oppenheimer, wartime director of Los Alamos, said: 'I am not qualified, and if I were qualified I would not be allowed, to give a detailed evaluation of the appropriateness of the use of atomic weapons against any or all such military targets; but one thing is very clear. It is clear that they can be used only as adjuncts in a military campaign which has some other components, and whose purpose is a military victory.

They are not primarily weapons of totality or terror, but weapons used to give combat forces help that they would otherwise lack. They are an integral part of military operations. Only when the atomic bomb is recognized as useful insofar as it is an integral part of military operations, will it really be of much help in the fighting of a war, rather than in warning all mankind to avert it.

Cohen's book Shame online 2nd ed. That of course was during the Korean War, which was eventually ended with a cease fire in due to an indirect threat from President Eisenhower to deploy nuclear weapons against China which was supporting the war effort of North Korea.

The first U. It was revised in May pages , and Nuclear Weapons Employment was issued in May pages. Instances appeared in war games where that delay ran into a number of days, sometimes permitting aggressor troops to reach densely populated friendly civilians areas where tactical nuclear strikes were precluded. McNamara, the U.

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We will use nuclear weapons whenever we feel it necessary to protect our vital interests. Our nuclear stockpile is several times that of the Soviet Union, and we will use either tactical weapons or strategic weapons in whatever quantities, wherever, whenever it is necessary to protect this nation and its interests.

Kennedy published a book in called The Strategy of Peace Harper and Brothers, New York; but note that the page numbers given for the quotations below are for the British edition, published by Hamish Hamilton, London, , where he explained pages why the normal strategic nuclear weapons are not adequate: "We must be prepared in this nation to fight an all-out nuclear war - or else we cannot deter an all-out nuclear attack upon us.

But it is not the only answer to all threats of Communist aggression. It cannot deter Communist aggression which is too limited to justify atomic war.

It cannot protect uncommitted nations against a Communist takeover using local or guerrilla forces. It cannot be used in so-called 'brush-fire' peripheral wars. In short, it cannot prevent the Communists from gradually nibbling away at the fringe of the Free World's territory and strength, until our security has been steadily eroded in peacemeal fashion - each Red advance being too small to justify massive retaliation with all its risks.

And history demonstrates that this is the greater threat - not an all-out nuclear attack.

They have approximately 17 pupils per teacher, we have The ten-year curriculum includes, on a compulsory basis, five years of physics, five years of biology, four years of chemistry, one year of astronomy, and ten years of mathematics Few, if any, twelve-year curricula in America cover as much.

In fact, more than half of our high schools do not teach any physics at all.

In the last year for which statistics are available, we produced only new physics teachers - although we have at least 28, high schools. The Russians are graduating ten times as many engineers as they did a generation ago - and at a rate two and one half times greater than the United States. They have enrolled and are graduating more scientists. We can sit back and wait for the Russian system to collapse. We can hope that education will be their undoing [leading to rebellion against Communist authority, i.

We can believe that our system will prevail On the other hand, we could compete with the Russians by imitating them. In Little Feller I a live Davy Crockett warhead was fired from a millimeter launcher Operation Ivy Flats and detonated at a height of burst of 20 feet some 9, feet 1.

The test was the last atmospheric detonation at the Nevada test site, and was observed by Attorney General Robert F. Kennedy and presidential adviser General Maxwell D. Taylor seen above in stills from the film of Operation Ivy Flats, which was finally declassified on 22 December The 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.

The international ampere is 0.

Since the heat can be measured, the value of the electrical energy can be determined and it is found, in agreement with anticipation, that the heat liberated by the current in a given conductor is proportional to the quantity of electricity passing and to the difference of potential at the extremities of the conductor. The practical unit of electrical energy is, therefore, defined as the energy developed when one coulomb is passed through a circuit by an E.

The United States Bureau of Standards has recommended that the unit of heat, the calorie, should be defined as the equivalent of 4. Alternatively, it may be stated that one international volt-coulomb is equivalent to 0. Classification of Conductors. It is not easy to distinguish sharply between good and bad conductors, but a rough division is possible; the systems studied in electrochemistry are generally good conductors.

These may be divided into three main categories; they are: a gaseous, b metallic and c electrolytic. Gases conduct electricity with difficulty and only under the influence of high potentials or if exposed to the action of certain radiations.

Metals are the best conductors, in general, and the passage of current is not accompanied by any movement of matter; it appears, therefore, that the electricity is carried exclusively by the electrons, the atomic nuclei remaining stationary. This is in accordance with modern views which regard a metal as consisting of a relatively rigid lattice of ions together with a system of mobile electrons.

Metallic conduction, or electronic conduction, as it is often called, is not restricted to pure metals, for it is a property possessed by most alloys, carbon and certain solid salts and oxides. Electrolytic conductors, or electrolytes, are distinguished by the fact that passage of an electric current through them results in an actual transfer of matter; this transfer is manifested by changes of concentration and frequently, in the case of electrolytic solutions, by the visible separation of material at the points where the current enters and leaves the solution.

Water, alcohols, pure acids, and similar liquids are very poor conductors, but they must be placed in this category. The second class of electrolytic conductors consists of solutions of one or more substances; this is the type of conductor with which the study of electrochemistry is mainly concerned.

The most common electrolytic solutions are made by dissolving a salt, acid or base in water; other solvents may be used, but the conducting power of the system depends markedly on their nature. Conducting systems of a somewhat unusual type are lithium carbide and alkaline earth nitrides dissolved in the corresponding hydride, and organic acid amides and nitro-compounds in liquid ammonia or hydrazine.

The distinction between electronic and electrolytic conductors is not sharp, for many substances behave as mixed conductors; that is, they conduct partly electronically and partly electrolytically. Fused cuprous sulfide conducts electronically, but a mixture with sodium or ferrous sulfide also exhibits electrolytic conduction; a mixture with nickel sulfide is, however, a pure electronic conductor.

Although pure metals conduct electronically, conduction in certain liquid alloys involves the transfer of matter and appears to be partly electrolytic in nature. The Phenomena and Mechanism of Electrolysis. The passage of current through solutions of salts of such metals as zinc, iron, nickel, cadmium, lead, copper, silver and mercury results in the liberation of these metals at the cathode; from solutions of salts of the very base metals, e.

If the anode consists of an attackable metal, such as one of those just enumerated, the flow of the current is accompanied by the passage of the metal into solution. When the anode is made of an inert metal, e. The decomposition of solutions by the electric current, resulting in the liberation of gases or metals, as described above, is known as electrolysis.

Mechanism of Grotthuss conduction The first definite proposals concerning the mechanism of electrolytic conduction and electrolysis were made by Grotthuss ; he suggested that the dissolved substance consisted of particles with positive and negative ends, these particles being distributed in a random manner throughout the solution.

When a potential was applied it was believed that the particles molecules became oriented in the form of chains with the positive parts pointing in one direction and the negative parts in the opposite direction Fig. It was supposed that the positive electrode attracts the negative part of one end particle in the chain, resulting in the liberation of the corresponding material, e. Similarly, the negative electrode attracts the positive portion of the particle, e.

The residual parts of the end units were then imagined to exchange partners with adjacent molecules, this interchange being carried on until a complete series of new particles is formed Fig. These are now rotated by the current to give the correct orientation Fig. The chief objection to the theory of Grotthuss is that it would require a relatively high E.

Although the proposed mechanism has been discarded, as far as most electrolytic conduction is concerned, it will be seen later p. In order to account for the phenomena observed during the passage of an electric current through solutions, Faraday assumed that the flow of electricity was associated with the movement of particles of matter carrying either positive or negative charges.

These charged particles were called ions; the ions carrying positive charges and moving in the direction of the current, i. The function of the applied E. It may be noted that since hydrogen and metals are discharged at the cathode, the metallic part of a salt or base and the hydrogen of an acid form cations and carry positive charges.

The acidic portion of a salt and the hydroxyl ion of a base consequently carry negative charges and constitute the anions.

Illustration of electrochemical terms Although Faraday postulated the existence of charged material particles, or ions, in solution, he offered no explanation of their origin: it was suggested, however, by Clausius that the positive and negative parts of the solute molecules were not firmly connected, but were each in a state of vibration that often became vigorous enough to cause the portions to separate.

These separated charged parts, or ions, were believed to have relatively short periods of free existence; while free they were supposed to carry the current.

According to Clausius, a small fraction only of the total number of dissolved molecules was split into ions at any instant, but sufficient ions were always available for carrying the current and hence for discharge at the electrodes. Since no electrical energy is required to break up the molecules, this theory is in agreement with the fact that small E.

The Electrolytic Dissociation Theory. 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.

The proportion of active, or dissociated, molecules to the total number of molecules, later called the degree of dissociation, was considered to vary with the concentration of the electrolyte, and to be equal to unity in dilute solutions. The latter author had shown that the ideal gas law equation, with osmotic pressure in place of gas pressure, was applicable to dilute solutions of non-electrolytes, but that electrolytic solutions showed considerable deviations.

For example, the osmotic effect, as measured by depression of the freezing point or in other ways, of hydrochloric acid, alkali chlorides and hydroxides was nearly twice as great as the value to be expected from the gas law equation; in some cases, e. This result is clearly in agreement with the views of Arrhenius, if the ions are regarded as having the same osmotic effect as uncharged particles.

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.

An Introduction to Electrochemistry

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.NBW Yon. For example, the osmotic effect, as measured by depression of the freezing point or in other ways, of hydrochloric acid, alkali chlorides and hydroxides was nearly twice as great as the value to be expected from the gas law equation; in some cases, e.

The chief objection to the theory of Grotthuss is that it would require a relatively high E. Illustration of electrochemical terms Although Faraday postulated the existence of charged material particles, or ions, in solution, he offered no explanation of their origin: it was suggested, however, by Clausius that the positive and negative parts of the solute molecules were not firmly connected, but were each in a state of vibration that often became vigorous enough to cause the portions to separate.

Properties and commercial uses of these are mentioned. 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. Isolation and purilication processes are discussed, and a few of the well-known processes of dispersion and the formation of derivatives and modifications, such as cellulose nitrate, acetate, and ethyl cellulose, are discussed briefly.

The Phenomena and Mechanism of Electrolysis. The first U.