Journal Archive Collections

Permanent URI for this communityhttp://localhost:4000/handle/123456789/16937

Browse

Author: search.filters.author.Paterson, Russell

Search Results

Now showing 1 - 8 of 8
  • No Thumbnail Available
    Item
    Transport in Aqueous Solutions of Group IIB Metal Salts at 298.15 K Part 2.—Interpretation and Prediction of Transport in Dilute Solutions of Cadmium Iodide : An Irreversible Thermodynamic Analysis
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (11), 1977) Paterson, Russell; Anderson, John; Anderson, Stephen S; Lutfullah
    The transport data of Part 1 have been used to obtain the binary mobility coefficients (Lik) and corresponding resistance coefficients (Rik) of the salt in the range 0.05–0.60 mol dm–3. It is shown that these binary mobility coefficients are summations of the more fundamental mobility and coupling coefficients (lik) between the component ions of the complexed salt: Cd2+, CdI2–xx(x= 1, 2, 3, 4) and I–. The distribution of these complexes at each concentration have been obtained from stability constant data and used in an optimisation procedure to obtain equivalent ionic conductances of the complex ions at infinite dilution (λ°x). These data were used to estimate lik coefficients (using Pikal's method), to predict binary coefficients (Lik) and to predict the transport numbers, conductances and salt diffusion coefficients of the salt in dilute solutions. Predicted and observed data are in good agreement in dilute solutions.
  • No Thumbnail Available
    Item
    Transport in Aqueous Solutions of Group IIB Metal Salts at 298.15 K Part 1.—Isothermal Transport Properties of Cadmium Iodide
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1977, 73 (11), 1977) Paterson, Russell; Anderson, John; Anderson, Stephen S
    The isothermal transport properties of aqueous cadmium iodide solutions have been measured in the range 0.05–0.60 mol dm–3. Transport numbers (t+) and solvent-fixed diffusion coefficients of the salt (Dv) were obtained, the former potentiometrically using cadmium amalgam concentration cells, with transference, and the latter by interferometry, using Rayleigh optics. In addition, electrical conductance measurements were made. The data are compared with existing, but incomplete, literature sources. Attention is drawn to the negative transport number of cadmium obtained in more concentrated solutions (> 0.28 mol dm–3).
  • No Thumbnail Available
    Item
    Stability Constants for Cadmium Iodide Complexes in Aqueous Cadmium Iodide (298.15 K)
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (02), 1978) Lutfullah; Paterson, Russell
    In order to interpret the transport properties of aqueous cadmium iodide, the concentrations of free ions and complexes (CdU'n; n = 1,2, 3,4) were required. For this method the method of Reilly and Stokes was used. Potentiometric data of Bates and Bates and Vosburgh were used and overall stability constants fit, 2.66xl02; fl2, 1.42xl03; /?3, 1.11 x 10s and /?4, 7.71 x 105 were obtained. The concentrations of individual complexes were then calculated for cadmium iodide solutions in the concentration range 0.001-0.50 mol dm-3.
  • No Thumbnail Available
    Item
    Transport in aqueous solutions of group IIB metal salts at 298.15 K. Part 6.—Irreversible thermodynamic parameters for zinc chloride and verification of Onsager's reciprocal relationships
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (09-12), 1978) Agnew, Andrew; Paterson, Russell
    The isothermal vectorial transport properties of zinc chloride (conductance, transport number and salt diffusion coefficients) have been measured over the concentration range 0.1–3.5 mol dm–3 at 298.15 K. These data have been used to calculate mobility (Lik) and resistance (Rik) coefficients, using irreversible thermodynamic theory. Hittorf and concentration cell estimates of transport number have been used to verify the Onsager reciprocal relationships. The effects of self complexing in zinc chloride are illustrated by comparison with zinc perchlorate and other group IIB metal halides for which data are available.
  • No Thumbnail Available
    Item
    Transport in Aqueous Solutions of Group IIB Metal Salts at 298.15 K Part 5.—Irreversible Thermodynamic Parameters for Zinc Perchlorate and Verification of Onsager’s Reciprocal Relationships
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1978, 74 (09-12), 1978) Agnew, Andrew; Paterson, Russell
    The isothermal vectorial transport properties of zinc perchlorate have been measured over the concentration range 0.1–3.0 mol dm–3 at 298.15 K. Hittorf transport numbers were shown to agree with those measured earlier using concentration cells. Conductance and salt diffusion coefficients were also measured. These data were used to calculate mobility (Lik) and resistance (Rik) coefficients using irreversible thermodynamic theory. Analysis showed that the Onsager reciprocal relationships (O.R.R.) were obeyed.
  • No Thumbnail Available
    Item
    Investigation of the Transport Properties of a Quaternary Ammonium Anion Exchange Membrane: Part 1.- —Application of Irreversible Thermodynamics to the Chloride Form
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1974, 70 (12), 1974) McCallum, Colin; Paterson, Russell
    A detailed study of the transport properties of the chloride form of a strong base quaternary ammonium anion exchange membrane has been completed. Experimental determination of isotope diffusion coefficients and electrical, salt diffusion, and osmotic properties has been made. From these data a complete irreversible thermodynamic analysis of the system in 0.1 and 1.0 mol dm–3 sodium chloride solutions has been obtained. Using primarily the frictional coefficient treatment, it is shown that the kinetic interaction between membrane ions and fixed charge contributes to a very large degree in reducing ion mobility, but that this contribution is large primarily because the membrane has very large internal ionic molality and not due to ion association. Equally, although there is considerable evidence for water structure enforcement around quaternary ammonium ions in aqueous solution, there is no evidence for this effect in the membrane. Water-to-water friction is similar to that obtained in other membrane studies on cation exchangers and to aqueous electrolyte solutions. The terminal hydroxyl groups on the quaternary ammonium fixed charges of the A104 membrane may do much to modify the unique solvation of alkyl substituted analogues. Pressure permeability and osmotic coefficients obtained by calculation indicate that the membrane is almost ideally semi-permeable with a reflection coefficient, σ, of 0.99 and 0.97 in 0.1 and 1.0 mol dm–3 salt solutions, respectively, and has a very low salt permeability.
  • No Thumbnail Available
    Item
    Comparison of the Transport Properties of Normal and Expanded Forms of a Cation-exchange Membrane: Part 3—Application of Irreversible Thermodynamics and Nernst-Planck Theories to Membranes in Concentrated NaCl Solutions
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (11), 1972) Gardner, Colin R.; Paterson, Russell
    The Onsager mobility and frictional coefficients for the normal and expanded membranes have been calculated when the external solution was 1.0 M NaCl. The validity of a number of methods of approximation of minor coefficients is examined. The results have been reproduced using a ternary electrolyte calculation in which mobility coefficients for the salt-free membrane were combined with those of aqueous sodium chloride. Calculated transport measurements agree well with those obtained experimentally. Finally the validity and probable errors of the Nernst-Planck theory are examined.
  • No Thumbnail Available
    Item
    Comparison of the Transport Properties of Normal and Expanded Forms of a Cation-exchange Membrane: Part 2.—Self-diffusion and Electrical Properties of Membranes in the Sodium Form in Concentrated Sodium Chloride
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (11), 1972) Ferguson, Hugh; Gardner, Colin R.; Paterson, Russell
    The influence of shrinking and increasing salt uptake on the transport properties of normal and expanded membranes has been examined. Isotopic diffusion coefficients from sodium and chloride ions were found to be functions of changing tortuosity and membrane electrolyte molality. Tortuosity corrected coefficients agreed closely with those of sodium and chloride ions in aqueous sodium chloride at equal molalities. Diffusion coefficients for tritiated water were constant, when corrected for tortuosity, and equal to the diffusion coefficient of tritiated water in pure water. From electrical measurements, it is shown that the ratio of solvent-fixed velocities of sodium and membrane-sulphonate ions is constant over the experimental range of conditions. The sulphonate ion is more mobile than sodium on this frame of reference and similar in behaviour to chloride or nitrate in free aqueous solution. All data indicate the validity of a simple aqueous model for membrane transport phenomena.