Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Phenomenological theory of the kinetics of ultrasonic emulsification

A working model is given for the rate of ultrasonic emulsification, considering the dispersion at the interface (area A) and the coagulations in the volume V of the emulsion. A bimolecular coagulation leads to the equation c=c∞tanh bt;c∞=(Aα/Vβ)1/2;b=(Aαβ/V)1/2 while a monomolecular coagulation gives c=c∞{1-exp (-at)};c∞=Aα/Vβ;a=β. The experiments on the dependence of c∞, a and b upon A and V favour the bimolecular coagulation. The results are satisfactorily explained on general theoretical grounds.

Comparison of elasticity and shell-theory solutions for finite circular cylindrical shells

A finite circular cylindrical shell subjected to a band of uniform pressure on its outer rim was investigated, using three-dimensional elasticity theory and the classical shell theories of Timoshenko (or Donnell) and Flügge. Detailed comparison of the resulting stresses and displacements was carried out for shells with ratios of inner to outer shell radii equal to 0.80, 0.85, 0.90 and 0.93 and for ratios of outer shell diameter to length of the shell equal to 0.5, 1 and 2. The ratio of band width to length of the shell was 0.2 and Poisson's ratio used was equal to 0.3. An Elliot 803 digital computer was used for numerical computations.

Experimental evidence of the cavity theory of sorption-desorption hysteresis by a study of the effect of electric discharge on entrapped water in silica gel

With the use of the quartz fiber spring balance, sorptions and desorptions of water on silica gel at 30°C were studied and the permanent and reproducible hysteresis loop was obtained. At different points on the desorption curve forming the loop, the gel was subjected to high tension glow electric discharge. As a result of the electric discharge, the gel at any point on the desorption curve shifts to a corresponding point on the sorption curve. This is due to the release from the cavities of gel of the entrapped water held in a metastable state. The electric discharge has no effect on the gel at different points on portions of the desorption curve which coincide with the sorption curve and also on the sorption curve itself, indicating the absence of entrapped water in the gel in these regions. The results afford direct experimental evidence of the reality of the cavity theory of sorption-desorption hysteresis.

Four-dimensional current algebra from Chern-Simons theory

We study an abelian Chern-Simons theory on a five-dimensional manifold with boundary. We find it to be equivalent to a higher-derivative generalization of the abelian Wess-Zumino-Witten model on the boundary. It contains a U(1) current algebra with an operational extension.

Rotation sensitivity of Lau fringes: an analysis based on coherence theory

An analysis based on coherence theory is presented, which explains the experimentally observed rotation sensitivity of the contrast of Lau fringes obtained under spatially incoherent illumination.

Trapped waves in the neighborhood of a sonic-type singularity

A model equation is derived to study trapped nonlinear waves with a turning effect, occurring in disturbances induced on a two-dimensional steady flow. Only unimodal disturbances under the short wave assumption are considered, when the wave front of the induced disturbance is plane. In the neighbourhood of certain special points of sonic-type singularity, the disturbances are governed by a single first-order partial differential equation in two independent variables. The equation depends on the steady flow through three parameters, which are determined by the variations of velocity and depth, for example (in the case of long surface water waves), along and perpendicular to the wave front. These parameters help us to examine various relative effects. The presence of shocks in a continuously accelerating or decelerating flow has been studied in detail.

Molecular theory of solvation and solvation dynamics of a classical ion in a dipolar liquid

A microscopic theory of equilibrium solvation and solvation dynamics of a classical, polar, solute molecule in dipolar solvent is presented. Density functional theory is used to explicitly calculate the polarization structure around a solvated ion. The calculated solvent polarization structure is different from the continuum model prediction in several respects. The value of the polarization at the surface of the ion is less than the continuum value. The solvent polarization also exhibits small oscillations in space near the ion. We show that, under certain approximations, our linear equilibrium theory reduces to the nonlocal electrostatic theory, with the dielectric function (c(k)) of the liquid now wave vector (k) dependent. It is further shown that the nonlocal electrostatic estimate of solvation energy, with a microscopic c(k), is close to the estimate of linearized equilibrium theories of polar liquids. The study of solvation dynamics is based on a generalized Smoluchowski equation with a mean-field force term to take into account the effects of intermolecular interactions. This study incorporates the local distortion of the solvent structure near the ion and also the effects of the translational modes of the solvent molecules.The latter contribution, if significant, can considerably accelerate the relaxation of solvent polarization and can even give rise to a long time decay that agrees with the continuum model prediction. The significance of these results is discussed.

Gauge-invariant reformulation of an anomalous gauge theory

An anomalous gauge theory can be reformulated in a gauge invariant way without any change in its physical content. This is demonstrated here for the exactly soluble chiral Schwinger model. Our gauge invariant version is very different from the Faddeev-Shatashvili proposal [L.D. Faddeev and S.L. Shatashvili, Theor. Math. Phys. 60 (1984) 206] and involves no additional gauge-group-valued fields. The status of the "gauge" A0=0 sometimes used in anomalous theories is also discussed and justified in our reformulation.

Hamilton’s theory of turns and a new geometrical representation for polarization optics

Hamilton’s theory of turns for the group SU(2) is exploited to develop a new geometrical representation for polarization optics. While pure polarization states are represented by points on the Poincaré sphere, linear intensity preserving optical systems are represented by great circle arcs on another sphere. Composition of systems, and their action on polarization states, are both reduced to geometrical operations. Several synthesis problems, especially in relation to the Pancharatnam-Berry-Aharonov-Anandan geometrical phase, are clarified with the new representation. The general relation between the geometrical phase, and the solid angle on the Poincaré sphere, is established.

A molecular theory of collective orientational relaxation in pure and binary dipolar liquids

A molecular theory of collective orientational relaxation of dipolar molecules in a dense liquid is presented. Our work is based on a generalized, nonlinear, Smoluchowski equation (GSE) that includes the effects of intermolecular interactions through a mean‐field force term. The effects of translational motion of the liquid molecules on the orientational relaxation is also included self‐consistently in the GSE. Analytic expressions for the wave‐vector‐dependent orientational correlation functions are obtained for one component, pure liquid and also for binary mixtures. We find that for a dipolar liquid of spherical molecules, the correlation function ϕ(k,t) for l=1, where l is the rank of the spherical harmonics, is biexponential. At zero wave‐vector, one time constant becomes identical with the dielectric relaxation time of the polar liquid. The second time constant is the longitudinal relaxation time, but the contribution of this second component is small. We find that polar forces do not affect the higher order correlation functions (l>1) of spherical dipolar molecules in a linearized theory. The expression of ϕ(k,t) for a binary liquid is a sum of four exponential terms. We also find that the wave‐vector‐dependent relaxation times depend strongly on the microscopic structure of the dense liquid. At intermediate wave vectors, the translational diffusion greatly accelerates the rate of orientational relaxation. The present study indicates that one must pay proper attention to the microscopic structure of the liquid while treating the translational effects. An analysis of the nonlinear terms of the GSE is also presented. An interesting coupling between the number density fluctuation and the orientational fluctuation is uncovered.