The solubility of silver chloride was measured in solutions from 1 x 10^-5M. to 1 x 10^-1M. in chloride ion concentration. Ag^110 was used as a radiotracer to measure the solubility. Evidence for the formation of molecular silver chloride and silver dichloride complex anions was found. A least squares analysis of the experimental data was used to calculate the solubility product constant and the formation constants for the molecular species and the complex ions. The solubility product constant was determined to be 1.74 x 10^-10. The formation constant of the molecular species and the complex ion were calculated to be 1.84 x 10^3 and 1.53 x 10^5 respectively. The agreement of the solubility product constant with that determined by potentiometric measurements was very good. The formation constant of molecular silver chloride was investigated further by extraction with an organic solvent. Nitrobenzene was used as the solvent and the distribution coefficient for the molecular silver chloride in nitrobenzene and aqueous solutions was determined to be 0.32. Evidence was found for the extraction of the molecular species and not the silver ions. However, at high chloride concentrations HAgCl_2 appears to be extracted. By the use of the distribution coefficient, and the concentration of silver in the organic phase, the formation constant of the molecular species was determined to be 1.5 ± .5 x 10^3.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1963. / Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 69-71).

The complex species in silver chloride solutions have been investigated by solubility measurements and by ion exchange methods in this work. The solubility of silver chloride in solutions of varying chloride ion concentrations was determined by radioassay techniques. The method of least squares was used to evaluate the constants for the formation of the aqueous silver chloride and the dichloro-complex species; the values being 1.99 x 103 and 2.98 x 104, respectively, at 25.00°C. Aqueous solver chloride has been shown to be sorbed by Amberlite IR-120 from silver chloride solutions which have an ionic strength of 0.2. This sorption has been found to follow the Freundlich, as well as the Langmuir adsorption equations. The sorbed species is postulated to be associated silver chloride molecules, the degree of association being about 4, 5, or 6.

The thesis aims to develop an ISFET chip compatible miniaturized planar reference. Such planar reference electrode will be constructed by: silica / silica oxide / titanium / palladium / silver / silver chloride / saturated KCl agar / silica nitride / silica. For the size of the reference electrode is only 10mm (length), 5mm (width) and 1mm (height), which is diminished of hundred-fold to the traditional reference electrode. In addition to develop the fabrication techniques of the electrodes, this thesis will be devoted to systematic measuring and analyzing their stability, AC impedence, cyclic voltammery and electrochemical noise characteristics. The results show that the stability is inside 1mV, offset voltage is about -9 mV and the resistance of AC impedence is 400

This thesis devotes to develop a wafer-level packaging technique of the planar AgCl-based micro reference electrode and to investigate its various electrochemical characteristics (including the potential stability and offset voltage, AC impedance, cyclic-voltammetry analysis, electrochemical noise and reproducibility). The miniaturized all-solid-state reference electrode can integrated with many biomedical or biochemical sensors for substantially reduce the dimension of the whole sensing system and improve the commercial capability of portable detecting products. This study reports firstly a smallest module of the micro reference electrode with dimension only about 9 mm (L) ¡Ñ 6 mm (W) ¡Ñ 1 mm (H) in the worldwide using the silicon bulk-micromachining technology, thin film deposition and chloridation techniques. The packaged reference electrode module is constructed by two bonded wafers with different functions. One wafer of this module is defined as ¡§electrode chip¡¨ and it has a Ti/Pd/Ag/AgCl planar quasi-reference electrode deposited on its surface. Another wafer is called as ¡§packaging chip¡¨ and it has two bulk-micromachined silicon cavities for the filling/sealing of 1.33 ~ 6.40 £gL KCl-gel (as the salt-bridge of electrode) and electrical connection. Many electrochemical characteristics of the encapsulated solid-state micro reference electrode are tested and improved for the commercial applications. Including a very stable cell potential (<4 mV in 30000 sec.), an approximately zero offset-voltage, a low AC impedance (1~20 K£[), and high reproducibility (drift less than 3~8 mV in 30000 sec. and the range of offset voltage is -6 ~ 3 mV) of the packaged micro reference electrode are demonstrated. Furthermore, stable CV curve of the packaged Ti/Pd/Ag/AgCl/KCl-gel reference electrode were proved by cyclic-voltammetry analysis and its low electrochemical noise spectrum was investigated and discussed in this work. Compared with the commercial reference electrode, the planar miniaturized AgCl reference electrode module developed in this thesis has displayed its many excellent characteristics and with a dimension only 250 times smaller than the conventional reference electrode.

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No description available.

Les premières photographies couleurs produites par Edmond Becquerel au Muséum d’Histoire naturelle à Paris en 1848 ont suscité un débat scientifique intense tout au long du XIXème siècle. La question de l’origine des couleurs de ces photographies a vu s’affronter les partisans d’une hypothèse pigmentaire et ceux d’une hypothèse interférentielle. Au cours du XXème siècle, cette question n’a pas été définitivement tranchée. Ce travail doctoral se propose d’appréhender la nature de ces images dites « photochromatiques » par une approche expérimentale. Nous nous sommes dans un premier temps intéressés aux étapes de sensibilisation du plaqué argent et d’exposition de la surface sensible aux rayonnements visibles, dans le but de répliquer le procédé Becquerel et de comprendre la photosensibilité de ces images. Les propriétés optiques des couches sensibles et colorées ont été caractérisées en spectroscopie UV-visible et mises en relation avec leurs compositions chimiques (étudiées en XAS) et leurs morphologies, de l’échelle micro- à nanométrique (étudiées en MEB et TEM). La grande sensibilité des échantillons aux faisceaux photoniques (UV-visible et rayons X) et électroniques a imposé un développement méthodologique afin de comprendre et de limiter les effets de sonde. Les résultats de cette recherche permettent de réfuter l’hypothèse de phénomènes interférentiels comme origine des couleurs des images photochromatiques, hypothèse qui prévaut dans la littérature depuis la fin du XIXème siècle. Les couches sensibles et colorées sont constituées de grains de chlorure d’argent micrométriques décorés de nanoparticules d’argent. Ces nanoparticules d’argent, que nous avons étudiées en EELS low loss, sont responsables de l’absorption dans le visible des couches sensibles et colorées par résonance de plasmons de surface. Ceci nous conduit à proposer une origine plasmonique aux couleurs des images photochromatiques, hypothèse discutée dans cette thèse. / The first colour photographs were produced in 1848 by Edmond Becquerel at the Museum of natural History in Paris. The origin of their colours motivated an intense debate between the scientists during the XIXth century. Two main hypotheses were proposed, namely a pigmentary hypothesis and an interferential hypothesis. Nowadays the question of the colours of those photochromatic images is still not settled and this doctoral research aims at addressing it by an experimental approach. We first studied the sensitizing of the silver plate and the exposure of the sensitive surface to light in order to replicate the Becquerel process and to gain information on the photosensitivity of these images. The optical properties of the sensitized and coloured layers were characterized by UV-visible spectroscopy and related to their chemical composition (studied by XAS) and their morphologies, from the micro to the nanoscale (studied by SEM and TEM). A methodological development was necessary to understand and overcome the sensitivity of the samples to photonic beams (UV-visible and X-rays) and electronic beams. The results allow us to reject the interferential hypothesis, which prevailed since the end of the XIXth century. The sensitized and coloured layers consist in micrometric silver chloride grains decorated by silver nanoparticles. Besides, these nanoparticles, which we investigated by low loss EELS, are responsible for the visible absorption of sensitized and coloured layers through surface plasmon resonance. We suggest that the photochromatic images colours have a plasmonic origin and hereby discuss this hypothesis.

Abstract The salt print is an important part of photography, both in its historic value and in the tonal range it can provide. This tonal range is greater than any other photographic printing process available to date attributed to the inherent masking ability of the metallic silver. However the intrinsic production problems have made it a 'forgotten' process. There are five key problems. 1. The difficulties in achieving the potential extensive tonal range. 2. The varying colour of the print. 3. Staining that appears in the print, during and after processing. 4. Instability and longevity of the salt print. 5. Contradictory and inaccurate information in material published on the salt print. Although the emphasis of the research is on exploring and controlling the colour and tonal range, the staining problems and stability of the print are also addressed. The materials used for contact negatives today vary in both capture and output, from analogue film processed in the traditional wet darkroom to a variety of transparent film printed from digital files. Inadequate density and tonal range can affect all types of negatives. To provide sufficient exposure time for the salt prints extended tonal range adjustments to the negative were necessary. These long exposures then converted sufficient silver salts to the image making metallic silver, utilising the intrinsic self-masking process. Ultimately this research has uncovered ways to control colour and tonal range and certain aesthetic qualities of the salt print, while simultaneously resolving some of the conflicts in published information. Accurate and consistent methods of processing eliminate staining, providing some stability to the print. The activities and steps carried out to make a salt print are manual; precise duplication is therefore almost unattainable. Nevertheless, although tests on a densitometer may display numeric differences, visual differences are barely noticeable.

No description available.