Chemistry Commons^™

Donor Properties Of Dimethylsulfoniumcyclopentadienylide And Tetramethylenesulfoniumcyclopentadienylide In Metal Complexes ; Part Ii. The Attempted Preparation Of Boron Tricyanide, Gary Scott Barney

Theses and Dissertations

Part I.--Complexes of dimethylsulfoniumcyclopentadientylide and tetramethylenesulfoniumcyclopentadienylide with metal ions were studied in order to determine the coordination site on the ylids. Infrared spectra indicate that the ylids are coordinated through the cyclopentadienyl ring in all complexes except for the Hg(CN)2 complexes. Coordination-of the HgI2, CdI2, ZnCl2, and AgNO3 complexes is through the number one position on the ring as suggested by NMR data. Infrared and NMR data strongly indicate that the ylids in the Hg(CN)2 complexes are coordinated through sulfur. Part II.--The only method given in the chemical literature for the preparation of boron tricyanide could not be duplicated in …

Estimations Of The Effective Electrolytic Surface Area Of Rough And Porous Silver Electrodes ; Ii. Potentiostatic Oxidation Of Silver In Alkaline Electrolyte, James Glenn Bearss

Theses and Dissertations

This dissertation is written in two sections. The first section deals with the development of methods for the estimation of the effective electrolytic surface area of rough and porous silver electrodes in alkaline electrolyte. Data are presented comparing the results of three different methods of surface area estimation. Model pore electrodes were also prepared and oxidized to study the reactions in a pore. Data for constant current oxidations of these electrodes is given. The second section deals with the potentiostatic oxidations of silver in alkaline electrolyte. Data are presented on the total charge acceptance versus applied potential for a potential …

A Thermodynamic Approach To The Study Of Phase Equilibria In The Sodium-Potassium Alloy System I. The Phase Diagram For Nak At Atmospheric Pressure ; Ii. High Pressure Phase Studies, Donald Ray Anderson

Theses and Dissertations

Ultra-pure reagents, platinum resistance thermometry and modern inert atmosphere glove box facilities have made possible a detailed examination of the NaK system at atmospheric pressure. A thermoanalytical study of solid-liquid phase equilibria in the NaK alloy system was conducted in the tetrahedral press to 55 kbars to investigate possible intermediate compound formation and shifting of the invariant points at various pressures. An expected shift in the eutectic composition to lower potassium content with an increase in the halt temperature on increasing pressure was confirmed. A merging of the meritectic and eutectic points at 343 ±2°K and 37 ±3 kbars occurred …

Thermodynamics Of Proton Dissociation And Metal Ion Complexation In Aqueous Solution. I, Cation Binding With Cyclic Polyethers: Significance In Ion Transport Processes. Ii, Proton Dissociation From Adenosine, Several Monosaccharides And Related Compounds. Iii, Proton Dissociation From Several Pyrimidines And Their Nucleosides At 10, 25 And 40°, Joseph Howard Ryttling

Theses and Dissertations

The log K, ΔH° and ΔS° values for the interaction of several metal ions with the two isomers of the cyclic polyether, 2,5,8,15,-18,21 hexaoxatricyclo[20.4.0.0^9,14]hexacosane are reported. The stability order found for alkali metal ion interaction with either isomer is identical to the order of ion permeability through reconstituted biological membranes for structurally related antibiotics. The size of the metal ion is critical in determining the extent of interaction. A calorimetric titration study of proton ionization from several monosaccharides and derivatives, pyrimidine bases and their nucleosides, adenosine and its derivatives, and cycloheptaamylose is described. The heats of reaction obtained in this …

The Catalytic Hydrogenation Of Benzodiazines.|Ni.|Pphthlazine.|Nii.|Pquinazoline, Danny Lee Elder

Theses and Dissertations

Quinazoline and phthalazine were hydrogenated at low pressure and temperature (60 psi, room temperature) and high pressure and temperature (2000 psi, 100°C, 150°C} in neutral and acidic solvents over 5% Pd/C, 5% Ru/C, 5% Rh/Al2O3 , 5% Rh/C, and 5% Pt/C. Chromatographic methods for determining the qualitative and quantitative composition of hydrogenation mixtures were developed. The compositions of quinazoline and phthalazine-hydrogenation mixtures were determined. Eight phthalazine-hydrogenation products were detected and isolated: (1) 1,2-dihydrophthalazine, (2) 1,2,3,4-tetrahydrophthalazine, (3) a,a'-diamino-o-xylene, (4) o-methylbenzylamine, (5) 1,3-dihydroisoindole, (6) o-xylene, (7 and 8) cis- and trans- 1,2-dimethylcyclohexane. These products were identified by isolating them from reaction mixtures …

Solid-Liquid Phase Equilibria Of The Sodium-Rubidium And Sodium-Potassium-Rubidium Alloy Systems, Chen-Chao Hsu

Theses and Dissertations

Thermal methods were used, to determine with high precision, the solid-liquid phase equilibria diagrams for the sodium-rubidium and sodium-potassium-rubidium systems. In the sodium-rubidium system, the results differ greatly from those of earlier works, especially near the eutectic composition where differences in freezing points as large as 25°K occur. A detailed search was made for possible intermetallic compounds (especially Na2Rb). Neither slow temperature cycling in the temperature range where compound formation could occur nor extended periods of annealing just above the eutectic temperature produced any evidence for compound formation in the sodium-rubidium system. A 2:1 (sodium to rubidium) sample was subjected …

Mechanism Of Water Transport Through Reverse Osmotic Membranes, Cheryl Kay Murphy

Theses and Dissertations

Cellulose acetate membranes show a higher permeability to water than to salt and are being used for desalination of salt water by reverse osmosis. Use of highly acetylated cellulose membranes give a higher salt rejection but also decrease flow rate of the water. The addition of very-short-chain substances or alkyl groups larger than one carbon atom to the cellulose membrane also decreases water flux. A proposed mechanism of transport through the membrane is that the water molecule is passed along the chain by hydrogen bonding with the acetyl groups, The NMR shows a change in the chemical shift of water …

Syntheses Via Modifications Of The Knorr-Paal Procedure :|Ba. Derivatives Of 2,6-Dioxa-10-Azatricyclo[5.2.1.0[Superscript 4,10]]Decane ; B. Highly Sterically Crowded 1,2,5-Trialkylpyrroles And Pyrrolidines, Weldron Severin Burnham

Theses and Dissertations

Earlier work in these laboratories on the heterotricyclic system 2,6-dioxa-10-azatricyclo[5.2.1.04,10]-decane, formed from 1,4-diketones and 2-amino-1,3-propanediols by a product-water-azeotroping procedure, was extended with the synthesis of analogous compounds, e.g., the 1,4,7-triethyl-, 1,7-dimethyl-4-isopropyl-1,7-diethyl-4-isopropyl-, 1,7-dimethyl-3- and 4-phenyl- compounds. The 1,7-dimethyl heterotricycle, the kinetically-controlled product, was accompanied by the thermodynamically-controlled product, 2-(2,5-dimethyl-1-pyrryl)-1,3-propanediol. The 1,7-diethyl heterotricycle was also accompanied by the isomeric pyrrole as were the 1,7-dimethyl-3- and 4-phenyl compounds. A scheme postulating a common intermediate is presented. The interesting analogous compounds, 1,7-dimethyl-2-oxa-6-thia-10-azatricyclo[5.2.1.04,10]decane, 1,4,7-trimethyl-2,6-dioxa-11-azatricyclo[5.3.1.04,11]undecane and 11-hydroxymethyl- and 11-methyl-9,13-dioxa-14- azatetracyclo[6.5.1.02,7 011,14]tetradeca-2,4,6-triene were also prepared. The syntheses in good yields of a considerable number of moderately to …

High Pressure, High Temperature Syntheses Of Selected Lanthanide-Tellurium Compounds, John Francis Cannon

Theses and Dissertations

High pressure, high temperature technics were employed to successfully synthesize HoTe1.7, ErTe1.7, TmTe1.7, LuTe1.7, YTe1.7, and LuTe3. The pressure-temperature regions in which synthesis of each compound is successful were determined. Pressures to 100 kbars concurrently with temperatures to 1200 °C were used in an attempt to prepare ScTe1.7 and ScTe3, but these efforts met with failure. X-ray studies of these new compounds confirmed that they are extensions of the LTe2-X (0≤x

The Thermodynamics Of Transition Metal Chelation In Dilute Aqueous Solution.|Ni.|Pthe Thermodynamics Of Interaction Of Serinate Ion With Divalent Co, Ni, Cu, Zn, And Cd Ions In Aqueous Solution.|Nii.|Pthe Calorimetric Standardization Of Dilute Ferrous Ion Solutions For Use In Determining 2,2'-Bipyridine, Joseph Willard Richards

Theses and Dissertations

Calorimetrically determined ΔH° values are given for the stepwise formation of chelate species between serinate ion and the divalent metal ions of Co, Ni, Cu, Zn, and Cd. These values of ΔH° are compared with those reported in the literature and were combined with values of ΔG° (log K) found in the literature to calculate values of ΔS°. These values of ΔG° and ΔS° are listed also. A new method of standardizing dilute ferrous ion solutions is reported. This procedure makes use of the thermometric titration technique to detect the equivalence point for the reaction of K_2Cr_2O_7 with ferrous ion. …

Determination Of Stability Constants At 25c For The Interaction In Aqueous Solution Of Serine With Co (Ii), Ni (Ii), Cd (Ii), Zn (Ii), And Cu (Ii) Ions, Liak Hwe Ma

Theses and Dissertations

Values of thermodynamic stability constants at 25°C for the complexes of serine with the metal ions. Co^2+, Ni^2+, Cd^2+, Zn^2+, and Cu^2+ were obtained from pH titration data. All measurements were made in aqueous solution, and data were obtained at three different ionic strengths for each metal ion studied. It was assumed that the activity of the zwitterion is unity. The effect of metal ion hydrolysis upon the log K values was taken into account for the calculations. For all the metal ions studied, stability constants for MA^+, MA_2, and MA_3^- were reported with the exception of copper (II) which …

A Study Of Reaction Parameters In The Hydrogenation Of Acetic Acid By Rhenium Heptoxide Catalyst, Victor L. Mylroie

Theses and Dissertations

Rhenium oxides as well as other rhenium compounds are known to display a broad spectrum of catalytic activity,^25 being resistant to attack by acids under nonoxidizing conditions, and showing a remarkable ability to resist poisoning which is a serious limiting factor in many commonly used catalysts. Rhenium catalysts are cheaper than the platinum metals with the exception of palladium. One of the most remarkable properties of the rhenium catalyst is the ability to catalyze the hydrogenation of carboxylic acids and amides to the corresponding alcohols and amines respectively. The carboxyl group (-COOH) is notoriously difficult to reduce catalytically and most …

High Pressure, High Temperature Syntheses Of Rare Earth Diantimonides And Th₃P₄ Type Polymorphs Of Rare Earth Sesquisulfides, Normal L. Eatough

Theses and Dissertations

The rare earths form series of compounds which are known for several elements but end abruptly or undergo a change of structure at some member of the series. The diantimonides are one such series. Sb-Sb repulsion becomes stronger as the rare earth size decreases and the previously known series ended at Sm. It was felt that high pressure would overcome the Sb-Sb repulsion and allow bonding to form stable or metastable compounds not possible by ordinary techniques. Synthesis studies were carried out on mixtures of antimony with all the rare earths except Pm and with Sc and Y. The known …

The Thermodynamics (Log K, [Delta]H°, [Delta]S°, [Delta]Cp°) Of Metal Ligand Interaction In Aqueous Solution.|Ni.|P Design And Construction Of An Isothermal Titration Calorimeter.|Nii.|Pthe Interaction Of Cyanide Ion With Bivalent Nickel, Zinc, Cadmium And Mercury.|Niii.|Pthe Interaction Of Glycinate Ion With Bivalent Manganese, Iron, Cobalt, Nickel, Copper, Zinc And Cadmium, Harlin Dee Johnston

Theses and Dissertations

A new isothermal titration calorimeter has been designed to facilitate the study of heats of reaction and heats of solution at constant temperature. With this calorimeter, endothermic or exothermic processes can be studied at temperatures constant to ±0.0002°C. Heat effects are compensated by balancing the heat effect of the process taking place in the calorimeter against a variable heat and a constant cooling Peltier device. The calorimeter was tested by measuring the heat of ionization of water and the heat of dilution of aqueous HClO_4 solutions. For these systems heats were measured to an accuracy of ±0.02 calorie. Log K, …

The Effect Of Thiamine And Its Antagonists On Plasma And Tissue Lactic Dehydrogenase In Rats, Dong Hwa Park

Theses and Dissertations

The lactic dehydrogenase activity in plasma and tissues was measured in the thiamine-deprived, the oxythiamine-treated and the pyrithiamine-treated rats as well as the control rats. The lactic dehydrogenase levels of brain and kidney were significantly increased by oxythiamine treatment. The enzyme activity in heart was markedly decreased only in the thiamine-deprived rats. Unlike the above tissues, the enzyme levels in liver were decreased by 29-44 per cent in all three types of thiamine deficiency, However, the enzyme activity in plasma was significantly increased only by pyrithiamine administration. The distribution patterns of lactic dehydrogenase isozymes were electrophoretically examined in these deficiencies. …

An Investigation Of Column Efficiency And The Relationship To Liquid Phase Distribution On Ultra-Low Loaded Glass Bead Gas Chromatographic Columns, Donald G. Nyberg

Theses and Dissertations

Studies have been made of column efficiencies, extra-column effects, the liquid phase mass transfer term (C_l), and liquid phase distribution at ultra-low liquid loadings on glass bead gas-liquid chromatographic columns. The advantages of using lightly loaded columns are described in detail along with a critical evaluation of the limitations of this liquid phase reduction ad infinitum. Theories have been presented by Giddings^22,23,25,30,32 which predict the mass transfer term (C_l) as a function of two extreme liquid phase distributions. The first equation assumes 100% "capillary" liquid held at the glass bead contact points and represents a very inefficient column. This prediction …

Thermodynamics Of Metal-Ligand Interactions In Solution I. The Thermodynamics Of Metal-Cyanide Interaction ; Ii. Application Of The Entropy Titration Technique To Metal-Ligand Systems ; Iii. Log K, [Delta]H And [Delta]S Values For The Interaction Of Sulfate Ion With Metal Ions ; Iv. Interaction Of Mercuric Cyanide With Thiourea In Water-Ethanol Solvent Mixtures, Delbert J. Eatough

Theses and Dissertations

Log K values, valid at zero ionic strength are reported for the interaction in aqueous solution of CN- with Ni2+ and Hg2+ at 10°, 25° and 40°C, and with Pd2+ at 25°C. ∆H° and ∆S° values valid at zero ionic strength and 25°C are also reported for the interaction of CN- with Hg2+ and for the reaction Pd(CN)42- + CN- = Pd(CN)53-. In connection with the study of Pd2+ - CN- interaction, log K values for the hydrolysis of Pd2+ to give PqOH+ and Pd(OH)2 and an E° value for the reaction Pd(s) = Pd2+ + 2e- are reported. A …

Secondary Reactions And Partial Rate Factors In The Sulfonation Of Chlorobenzene And Toluene, Ernest Arthur Brown

Theses and Dissertations

The sulfonation of chlorobenzene, chlorobenzene-benzene, and toluene-benzene mixtures by sulfur trioxide in liquid sulfur dioxide at -12.5° C. was studied to obtain isomer distribution and relative rate data. The isomer distribution for the reaction on chlorobenzene was determined by an isotope dillution technique. Relative rate experiments were conducted by sulfonating C14 labeled benzene in competition with nonradioactive chlorobenzene and toluene and the count rate of the products was used to determine product composition. Ultraviolet spectrophotometry was also used to investigate variations in isomer distributions as a function of sulfur trioxide concentration. The apparent relative rates of sulfonation (kX/kB) as calculated …

Refinements In The Isomer Distribution And Relative Rate Of Sulfonation Of Toluene And Hydrochlorination Of Olefins With Stannic Chloride Catalyst, David George Guillot

Theses and Dissertations

The sulfonation of toluene at -12.5° C. with sulfur trioxide in liquid sulfur dioxide was found to give 10.03 ± 0.20 % ortho, 0.73 ± 0.20 % meta and 89.24 ± 0.20 % para isomers. This isomer distribution was determined by isotope dilution analysis using sulfur-35 enriched sulfur trioxide. After dilution of aliquots of the neutralized sulfonation mixture with pure sodium salts of each of the isomers prepared from the corresponding toluidines, the isomers were converted to the p-toluidine salts, purified by recrystallization, and counted by liquid scintillation counting. The relative rate of sulfonation of toluene compared to benzene was …

The Synthesis Of 4-Spiro-2-Aryloxazolines Of Potential Pharmacological Interest, Paul Waddell Collins

Theses and Dissertations

Numerous and diverse physiological actions are found among 2-oxazoline compounds. No reports of the synthesis or biological testing of 4-spiro-2-aryl-2-oxazolines were found in the literature. On the basis of the known pharmacological activities of certain aza- and diazaspirans, it was felt that 4-spiro-2-aryl-2-oxazolines should possess medicinal activity. In particular, it was reasoned that the combination in a bicyclic spiro structure of the 2-oxazoline ring with rings systems commonly found in synthetic antitussive compounds might result in active antitussive agents.

The aim of this research was the synthesis of a series· of 2-aryl-2-oxazoline-4-spirocyclopentanes and a series of 1'-methyl-2-aryl-2-oxazoline-4-spiro-4’-piperidines. Six members were …

Thermodynamics Of Proton Ionization In Aqueous Solution I. A Precision Thermometric Titration Calorimeter ; Ii. Entropy Titration : A Calorimetric Method For Equilibrium Constant Determinations ; Iii. H And S Values For Carboxylic Acid Proton Ionization At 25c ; Iv. Site Of Proton Ionization From Adenosine, Lee D. Hansen

Theses and Dissertations

The design, construction, and calibration of a precision thermometric titration calorimeter is described. This calorimeter was tested by determining the enthalpy change for ionization of water. The result, 13.34 ±0.03 kcal/mole (standard deviation), is in exact agreement with the best literature values. This standard deviation indicates that, using this calorimeter, ΔH values can be determined with an accuracy of ±0.0.5 kcal/mole. A calorimetric procedure has been developed for the, simultaneous determination of the equilibrium constant, the enthalpy change, and the entropy change for a chemical reaction from a single titration (Entropy Titration). This procedure has been tested by determining pK, …

Properties Of Chlorophyll Derivatives Bonded To Polymers, Richard Grant Jensen

Theses and Dissertations

Two types of water-soluble complexes of chlorophyll a with organic polymers have been investigated: chlorophyll a coordinately bonded to poly 4-vinylpyridine and a chlorophyll derivative, Mg-chlorin e_6 phytyl methyl ester, covalently bonded to GANTREZ AN (poly (methyl vinyl ether/maleic anhydride) ). The first complex was observed upon dissolving chlorophyll a and poly 4-vinylpyridine in aqueous ethanol solutions. The Mg-chlorin e_6 diester-GANTREZ AN complex (chlorophyll a/polymer) was made by aminolysing the chlorophyll ring V with 1, 6-hexanediamine to give an intermediate product, Mg-chlorin e_6 -6-N-(6' -aminohexyl) carboxamide, phytyl methyl ester. This was attached to GANTREZ AN by linkage of the 6'-amine …

Thermodynamics Of Charge Transfer Complexes, Reed J. Jensen

Theses and Dissertations

Charge transfer complexes were studied spectrophotometrically in the liquid state by a modified Benesi-Hildabrand method. TiCl_4 - Benzene and TiCl_4 - diphenyl ether solutions were found to form contact charge transfer complexes, that is complexes with very weak and non-directional interactions. The systems TiCl_4 - anisole and TiCl_4 - diethyl ether form complexes of the types AD and AD_2 where A stands for TiCl_4 and D stand s for the organic donor. The formation constants for the complexes were, for the TiCl_4 - anisole, K_1 = 0.077, K_2 = 0.01; and TiCl_4 - diethyl ether, K_1= 3.0, K_2 = 1.0. …

A Thermodynamic Study Of (1) Ligand Replacement Reactions And (2) The Interaction Of Hgcl[Subscript 2](Aq) With Hydroxide Ion, Ethylenediamine, Glycinate Ion, And Methylamine, Jerry Alvin Partridge

Theses and Dissertations

A method is reported for determining the species formed in solution by ligand replacement reactions. Reactions in dilute aqueous solution were studied in which the Cl^- on HgCl_2(aq) was replaced by hydroxide ion, ethylenediamine, glycinate ion, and methylamine. The species formed by the replacement reactions were established through computer analysis of pH titration data. Various reaction sequences were proposed for each system and log K values were calculated for each sequence. The selection of the correct reaction sequence for each system was based on the premise that only when the correct sequence is proposed will consistent log K values be …

Hydrogenation Of 4-Methylcinnoline, William E. Maycock

Theses and Dissertations

The rapid expansion of knowledge of cinnoline chemistry since 1941 has not included the hydrocinnolines. Not one catalytic hydrogenation of a fully aromatic cinnoline had been reported. This thesis is an effort to enlarge knowledge of this particular area of cinnoline chemistry. The work is a natural outgrowth of that done at Brigham Young University on decahydroquinoxaline, both the cis- and trans- isomers having been prepared and characterized. 4-Methylcinnoline, prepared by the method of Jacobs, et.al., was hydrogenated in neutral and acidic ethanolic solutions at 2000-3000 psig. hydrogen pressure and 100-266°. The catalysts used were 5% palladium on alumina, ruthenium …

Metabolism Of Thiamine And The Effect Of Some Antagonists, Russel M. Bender

Theses and Dissertations

To investigate the possibility that thiamine has more than one vital role in the mammalian system, it was decided to use the antagonists pyrithiamine and oxythiamine, and to utilize carbon-14 labeled compounds to more effectively study the vitamin and the above-named antagonists. To make it more effective, we felt that perhaps differences between the localization of oxythiamine and pyrithiamine could be detected in the brain. We also considered and tested the possibility that either or both of the antagonists would alter the localization of thiamine. Essentially, two procedures were used in this study. One was a counting method and the …

Evaluation Of Methods Used In The Determination Of Stability Constants Of The Thallium (Iii)-Chloride System At Twenty-Five Degrees, Nelson Kent Dalley

Theses and Dissertations

The difficulties encountered in the determination of equilibrium constants in systems with small, not directly rneasureable free ligand concentrations are discussed. These difficulties are illustrated using the determination of the formation constants of the Tl(III)-Cl- system as a specific example. Four methods are used and evaluated in this study. They are (1) the corresponding solutions method, (2) the method of Fronaeus, (3) the solubility of AgCl in Tl(III) solution method and (4) the method of Hugus. A discussion and derivation of each of these methods is given. The first three methods given and free ligand concentration data from which formation …

A Calorimetric Study Of Metal Amino Acid Complexes In Aqueous Solution. I. The Copper (Ii) Glycine System. Ii. The Nickel (Ii) Glycine, Alanine And Phenylalanine Systems, Wilbur Orme Greenhalgh

Theses and Dissertations

Calorimeter values were obtained for the standard enthalpy change for the following reactions at 10,25, and 40 degrees C.: 1. The dissaciation of the amino acid, glycine, in the zwitterion form (HA) to give the basic form (A-) and a proton. 2. The reactions of copper (II) ion with glycine to form the Cu gly+ and Cu (gly)2 complexes. 3. The reactions of nickel (II) ion with glycine and alanine to form Ni gly+, Ni (gly)2, Ni al+, and Ni (al)2 complexes. For calorimetric enthalpy calculations, the initial and final concentrations of all species in the calorimeter must be known; …

I. Preparation And Properties Of Alkyl And Aryl Substituted Thioquinazolines And Sulfoxides ; Ii. An Investigation Of The Quinazoline 3-Oxide--1,4-Benzodiazepine 4-Oxide Rearrangement, Marvin C. J. Kuchar

Theses and Dissertations

I. The quinazolines, a branch of the benzodiazine class of aromatic nitrogen hetercycles, do not occur to any great extent in naturally occurring compounds. The discovery of the antimalarial febrifugine and its structure elucidation led to the preparation and investigation of a host of new quinazolines in the search for new and more effective antimalarials. Most of the present body of information governing the quinazolines arose out of these synthetic studies. The present study has been accomplished with a four-fold purpose in mind: (1) to investigate the susceptibility of chloroquinazolines to nucleophilic displacement reactions by thiols or their salts, (2) …

Thermodynamics Of I) Metal Cyanide Coordination, Ii) Water Formation, And Iii) Metal Halide Coordination, John Dewey Hale

Theses and Dissertations

ΔH values for the formation of Ni(CN)4(aq)= have been determined calorimetrically at 25° using a simple calorimeter and a thermometric titration procedure at high and low ionic strengths, respectively. Extrapolation of these ΔH values to infinite dilution resulted in a ΔH° value of -42.7 kcal./mole. Combination of ΔH° and ΔF° values gives a ΔS° value of -5.5 e.u. for Ni(CN)4(aq)= formation. A value of +70 e.u. is calculated for the ionic entropy of Ni(CN)4(aq)=. A preliminary investigation of the Zn(CN)4(aq)= system indicated the existence of zinc cyanide complexes other than Zn(CN)4= and allowed calculation of an approximate ΔH° value of …