scholarly journals VI. On chemical dynamics and statics wider the influence of light

The nature of the forces which come into play when substances react one upon another chemically, is a problem which has specially engaged scientific minds during the last century. During the second half of that period chemical statics and dynamics have developed into a veritable science. The general law governing the velocity of chemical reaction and chemical equilibrium in homogeneous systems is now known as the law of mass action, and was to a great extent foreseen by Berthollet. In heterogeneous systems the law concerning the velocity of physical or molecular transformation also proves to be of a general and simple nature; the velocity being directly proportional to the surface of contact of the reacting parts of the heterogeneous systems and to the remoteness of the system from the point of equilibrium. The velocity of chemical reaction and chemical equilibrium in heterogeneous systems represent no phenomena sui generis , the laws, concerning them being only combinations of the above two laws. The laws relating to equilibrium found their rational explanation and foundation in the thermodynamic researches of Horstmann, and more fully in those of W. Gibbs and van’t Hoff, whilst the laws applying to the velocity of reaction in homogeneous systems are the result of van’t Hoff’s thermodynamic considerations. In all the above researches the phenomena of the velocity of chemical reaction and of chemical equilibrium are the outcome of those intrinsic properties of matter, always existent in and inseparable from it, which we usually call chemical affinity or chemical potential. It is known, however, that a system can be brought into a state of reaction, and that new systems and new equilibria can be formed, when energy from an external source, such as light or electricity, is introduced into it. The effect of an electric current upon a chemical system, e.g ., is determined by Faraday’s law of electrolysis, whilst the thermodynamic connexion between chemical and electrical (and gravitation) energy has been developed by W. Gibbs.

1902 ◽  
Vol 70 (459-466) ◽  
pp. 66-74

Since the second half of the last century chemical statics and dynamics have developed into a veritable science of their own. The general law governing velocity of chemical reaction and chemical equilibrium in homogeneous systems is now known as the law of action of mass; the law governing velocity of physical or molecular transformations in heterogeneous systems proves also to be of a general and simple nature: the velocity is directly proportional to the surface of contact of the reacting parts and to the remoteness of the system from the point of equilibrium;! the velocity of chemical reaction in heterogeneous systems and chemical equilibrium in heterogeneous systems represent no phenomena sui generis , and the laws governing them are only combinations of the other two laws mentioned.


1905 ◽  
Vol 74 (497-506) ◽  
pp. 369-378 ◽  
Author(s):  
Meyer Wilderman ◽  
Ludwig Mond

In my paper “On Chemical Statics and Dynamics” (‘Phil. Trans.,' A, vol. 199, 1902, p. 337), and especially ‘Zeit. Physik. Chemie,' voL 42, 1902, pp. 316—335, I deduced, from thermodynamics, the laws experimentally found by me for velocity of chemical reaction, and for chemical equilibrium under the action of light, from the fundamental conception that the chemical potential of substance in light and in the dark is different, becoming greater in light. The foundation for this conception was that two metallic plates immersed in a liquid and connected to a circuit form a “galvanic” combination, when one plate is exposed to light while the other is kept in the dark; and, according to Gibbs’ equation, v " — v ' = α a ( μ ' a — μ " a ), no galvanic cell could be formed, unless the chemical potentials at the two electrodes were different in light and in the dark.


The following is a summary of the different subjects dealt with in the paper. (1) Further evidence is given that velocity of chemical reaction and chemical equilibrium in homogeneous systems follow under the action of light the laws of mass action. (2) Experimental proof that the E. M. F. produced by light in the different systems consists of two E. M. F.’s, viz.: one created by light at a constant temperature due to the variation of chemical potential, and a thermo-E. M. F. simultaneously produced by the heating effect of the light, and due to the variation of the chemical potential with temperature (quantitative separation of the total E. M. F. into the two E. M. F.’s, and determination of the value of each E. M. F. in the different systems).


The theory of condensing systems of J.E. Mayer is generalized for a mixture of an arbitrary number of gases. Strict equations for chemical equilibrium in a mixture of gases are derived. For sufficiently small pressures they reduce to the law of mass action.


In devising methods for determining the velocity of any chemical reaction there are two experimental problems which invariably arise : (1) To arrange that the chemical system under investigation be made initially unstable in a period of time that is negligibly short in comparison with that taken by the chemical reaction. (2) To record from time to time the stages reached by the system (during its passage from the initial unstable state to the final stable condition wherein the several reacting substances are in chemical equilibrium) by means of methods which take a negligibly short time in comparison with that taken by the chemical reaction. A perusal of the literature shows that previous investigators have, in the main, restricted themselves to the study of slow reactions, such as may require many minutes or even hours to reach completion. In such cases, both requirements which we have mentioned can be easily met. For the production of the initially unstable condition can be achieved without difficulty by merely mixing the several reacting substances together in proportions far removed from those which prevail when equilibrium has been attained. The time required by the mixing operation can be reduced to a few seconds, and can therefore be neglected when dealing with a process which may last many minutes or even hours. The slow reactions possess a further attraction, in that the procedure for estimating the concentrations of the several reactants at different stages during the progress of the reaction need not be a hurried one. This permits the use of a wide variety of methods, e. g ., polarimetry as in the study of the inversion of sucrose, ordinary titration as in the saponification of esters, and separation of one of the constituents as a gas phase as in the decomposition of diazo-acetic ester by water, i. e ., N 2 . CHCOOC 2 H 5 +H 2 O→OHCH 2 . COOC 2 H 5 +N 2 (gas phase).


2009 ◽  
Vol 15 (5) ◽  
pp. 578-597
Author(s):  
Marcello Farina ◽  
Sergio Bittanti

Sign in / Sign up

Export Citation Format

Share Document