Electrochemical determination of the standard Gibbs free energy change of the graphite-Oxygen reactions

A calcia doped zirconia solid oxide electrolyte galvanic cell was investigated in the temperature range of 700–950°C to directly and more accurately measure the standard Gibbs free energy change of the following reactions: $\text{CO(g) +}\text{1}\text{2}\text{O}{}_2\text{(g) = CO}{}_2\text{(g)}$C_(graphite) + CO₂(g) = 2 CO(g). The results obtained in the present investigation are well within the scatter band of the calorimetric and spectroscopic data.     

Highly conducting polymers based on polyacetylene hydrogen sulphate: Preparation and stability studies

Oxidation of polyacetylene with sulphuric acid, leading to the formation of highly conducting polymer films, was studied under varying conditions. It was found that the highest quality films were obtained in the gas phase reaction with 98% H₂SO₄ where the $\text{H}{}_2\text{SO}{}_4\text{H}{}_2\text{O}$ ratio is crucial for correct doping. The reaction product can be formulated as [CH(HSO₄)_y]_x. Oxygen attack leads to the irreversible degradation of the polyene chain and reaction with H₂O results in compensation of the dopant anions.     

Oxidation of hydrogen sulfide over microporous carbons

Microporous carbon of high purity was produced by the carbonization of Saran at 900° followed by activation in either CO₂ at 900°, O₂ at 300°, or air at 425°. The activated carbons were characterized using N₂ adsorption at ?195° CO₂ adsorption at 25°, and mercury and helium displacements. Hydrogen sulfide oxidation (at H₂S pressures between 0.4–3.8 Torr) by O₂ (in excess of stoichiometric amount) was studied between 100–160° using a microbalance, that is by weighing the build-up of sulfur on the carbon. The predominant reaction, $\text{H}{}_2\text{S +}\text{1}\text{2}\text{O}{}_2\text{→}\text{1}\text{2}\text{S}{}_2\text{+ H}{}_2\text{O}$ was first order in H₂S concentration and independent of O₂ concentration. The rate was only slightly reduced by sulfur build-up to at least 36%, by weight, on the carbon. The oxidation rate was significantly higher over the O₂-activated carbon than over the CO₂-activated carbon. Throughout the studies, oxidation rates could be correlated with area active to O₂ chemisorption. It is concluded that H₂S oxidation proceeds via rapid dissociative chemisorption of oxygen on carbon sites followed by reaction with H₂S. Rates of H₂S oxidation were also studies over commercial, granular activated carbons of significant ash contents.     

Kinetics of the graphite-oxygen reaction near 1000°K

The kinetics of oxidation of spectroscopic grade polycrystalline graphite have been studied by a flow method which allowed the partial pressure of oxygen (P_o2) to be changed abruptly during the course of the reaction. The changes were made in two alternative ways: by changing the total pressure of an oxygen/nitrogen mixture of constant composition or by changing the composition at constant total pressure. After the effect of diffusion resistance on the rate had been shown to be negligible and the effects of self-heating, burn-off and traces of gaseous impurities allowed for, the order of reaction (ń in the empirical expression: rate α ) was found to vary from 0.34 (at 993°K and mean ) to 0.19 (at 963°K and mean P_o2 = 245 torr). In certain circumstances, the response of the rate to changes in P_o2 is subject to a “memory” effect. This is attributed to fast, diffusion-controlled chemisorption of a minute amount of hydrogenous impurity on part of the active surface of the graphite.     

Absorption of sulphur dioxide by sodium humates

As part of a programme for assessing the potential of basic humates as stack gas scrubbing media, the reaction of sodium salts of coal derived humic acids (HA) with sulphur dioxide was investigated. The principal absorption mechanism was found to be acid-base:

$\text{Na-HA(aq) + SO}{}_2\text{(g) + H}{}_2\text{O}\text{?}\text{HA(s) + HSO}{}^{\mathrm{t-}}{}_3\text{(aq) + Na}{}^{\mathrm{+}}\text{(aq)}\text{Soluble sodium}\text{Insoluble humic}\text{humate}\text{acid}$

However, formation of a sulphur dioxide-HA ‘complex’ was observed under conditions (low pH, high temperature) which favoured conversion of a significant fraction (> 5%) of dissolved sulphites to the SO₂(aq) ‘H₂SO₃’ form. Greater complexation of SO₂(aq) was observed for HA preparations which had been stored under basic conditions for periods up to two years. Reversibility of absorption and desorption was demonstrated. Similar experiments with hydrogen sulphide revealed no significant reaction with sodium or iron(III) humates.     

Nucleophilic substitution onto poly(methylmethacrylate): 4. Dilute solution properties of substituted polymethacrylates

The morphological and hydrodynamic properties of a series of homogeneous fractions of substituted poly(methylmethacrylate) (A units) bearing keto-β-functional groups (B units) of the general structureCOCH₂R, with R = SO_xCH₃ (x = 1,2) or SO₂N(CH₃)₂, were investigated by intrinsic viscosity, light scattering and partial specific volume measurements in dimethylformamide (DMF) solution at 25°C. For molar substitution degrees $\text{DS}{}_{\mathrm{m}}\text{< 0.5}$, the copolymers behave as flexible random coils. The Stockmayer-Fixman-Yamakawa analysis of the $\text{[η]-}\text{M}\text{?}{}_{\mathrm{w}}$ data leads to slightly higher unperturbed dimensions K_o and steric factor σ than those for PMMA, and to stronger chain expansion as a result of the weak hydrogen bonding between DMF and COCH₂R units and a positive X_AB interaction parameter. For $\text{DS}{}_{\mathrm{m}}\text{> 0.5}$ however, copolymers bearing COCH₂SO₂N(CH₃)₂ groups behave as worm-like chains, as derived from the Fujii-Yamakawa analysis of the $\text{[η]-}\text{M}\text{?}{}_{\mathrm{w}}\text{-}\text{v}\text{?}$ data: the persistence length increases from 380 to 570 Å within the $\text{DS}$_m range 0.57–0.75. This transition from a random coil to a worm-like chain for $\text{DS}{}_{\mathrm{m}}\text{> 0.5}$ was tentatively correlated with the accumulation of B units in sterically hindered and self-associated short blocks of average length l_B ? 1.6 which provide drastically increased rigidity to the copolymer chain.     

Physical characterization of suspension-crosslinked polystyrene particles and their sulphonated products: 2. Ionic networks

Strong cationic resins have been prepared from isoporous polystyrene networks in bead form with H₂SO₄ and HSO₃Cl as sulphonating agents. The effect of the reaction time of H₂SO₄ sulphonation on ion exchange capacity has been examined. The polymer-solvent interaction parameter, X, with aqueous electrolyte solutions has been calculated after minimization of electrostatic repulsions. The average molecular weight per crosslinked unit, $\text{M}\text{?}{}_{\mathrm{<mtext>c</mtext>}}$ has been measured after sulphonation and an estimation of formation of sulphone-type crosslinks has been attempted. The average size of the network structure, r_c, has been calculated as a function of the ionic strength of aqueous electrolyte solutions for networks of different molecular weight per crosslinked unit, $\text{M}\text{?}{}_{\mathrm{<mtext>c</mtext>}}$. The ion exchange capacity of the prepared resins has been measured.     

Branched poly(ethylene terephthalate) correlations between viscosimetric properties and polymerization parameters

Samples of poly(ethylene terephthalate) (PET) modified with small amounts of trimesic acid groups and hence containing long chain branching have been prepared. From the content of trifunctional modifier and from the experimental value of the extent of reaction, the weight-average molecular weight $\text{M}\text{?}{}_{\mathrm{w}}$ and branching density $\text{B}\text{?}{}_{\mathrm{w}}$ have been calculated, assuming that all the end-groups are equally reactive and intramolecular reactions are absent. The values of $\text{M}\text{?}{}_{\mathrm{w}}$ and $\text{B}\text{?}{}_{\mathrm{w}}$ have been correlated with the experimental values of intrinsic viscosity [η] and the Newtonian melt viscosity η₀. General relations of the following type have been obtained:

$\text{f}{}_1\text{([η],}\text{M}{}_{\mathrm{w}}\text{,}\text{B}{}_{\mathrm{w}}\text{) = 0; f}{}_2\text{(η}{}_0\text{,}\text{M}{}_{\mathrm{w}}\text{,}\text{B}{}_{\mathrm{w}}\text{) =0; f}{}_3\text{(η}{}_0\text{, [η],}\text{B}{}_{\mathrm{w}}\text{) = 0; f}{}_4\text{(η}{}_0\text{, [η],}\text{M}{}_{\mathrm{w}}\text{) = 0;}$

In particular, [η] and η₀ increase on increasing $\text{M}\text{?}{}_{\mathrm{w}}$ and decrease on increasing $\text{B}\text{?}{}_{\mathrm{w}}$, but, at equal [η] values, η₀ increases with $\text{B}\text{?}{}_{\mathrm{w}}$. Through the last relation, the reliability limits of which should be experimentally checked, and from measurements of [η] and η₀, it is possible to calculate $\text{M}\text{?}{}_{\mathrm{w}}$ of a branched PET.     

Chemical beneficiation of coal with aqueous hydrogen peroxide/sulphuric acid solutions

The removal of sulphur and ash from coal treated with aqueous hydrogen peroxide/sulphuric acid solutions has been studied at ambient temperature, under a variety of experimental conditions. Almost complete elimination of the sulphate and the pyritic sulphur was observed in most cases, as well as substantial reduction in the ash content. The other components of the organic coal matrix were not affected to a significant extent, indicating high selectivity of the $\text{H}{}_2\text{O}{}_2\text{H}{}_2\text{SO4}$ system towards sulphur oxidation. An optimal H₂SO₄ concentration was established, above which the acid was found to have an adverse effect on the oxidation of pyrite by hydrogen peroxide.     

Gelation in the reactions of aliphatic di-isocyanates with triols

Gelation in reactions of Niax triols with hexamethylene and decamethylene di-isocyanates has been studied. The gel points occur at extents of reaction in excess of those predicted by Flory-Stockmayer theory. The excess, intramolecular reaction increases with dilution and with decreases in the molecular weights of the reactants. Kilb's theory of gelation does not explain the results, but a semi-quantitative explanation is found in terms of a combination of Frisch's and Kilb's theories. In this, λ, the intramolecular branching parameter of Frisch, is given by the equation $\text{λ =}\text{const}\text{.v}{}^{\mathrm{<mtext>?</mtext><mtext>3</mtext><mtext>2</mtext>}}\text{(}\text{OH}{}_0\text{+}\text{NCO}{}_0\text{)}{}^{\mathrm{?1}}$, with v the number of bonds in the smallest ring which can form.     

A mechanistic study of hydrogenation of coal. 2.

In Part 1 the authors reported that liquefaction of coal by hydrogenation in the presence or absence of vehicle and with or without catalyst progresses with characteristic variations of the reaction order. In the present paper, the roles of temperature, hydrogen, vehicle and catalyst have been studied using a free-radical scavenger such as p-benzoquinone or iodine. Based on these results, a set of characteristic reactions has been identified from which the following overall rate equation has been derived: $\text{d[P}{}_{\mathrm{m}}\text{]}\text{dt}\text{= β}{}_1\text{[C] + β}{}_2\text{[C]}{}^2\text{+ β}{}_3$ where [P_m] denotes gas, and benzene-soluble products, [C] represents the percentages of organic matter in coal and benzene insoluble intermediates, and β₁, β₂ and β₃ are constants. The rate equation thus explains the experimentally observed variation of the reaction order, which depends on the predominance of a particular group of reactions. It has been postulated that pyrolysis is the main driving force, and that hydrogenation of coal either with gaseous hydrogen or by hydrogen-donating vehicle is basically influenced by reactions involving free radicals.     

Effect of SO3 on formation and hydraulic reactivity of belite

SO₃ accelerates the formation of belite between 1100 and 1300°C. Its effeciency rests on the permanent generation of CaO in statu nascendi by the equilibria $\text{CaSO}{}_4\text{?}\text{CaO + SO}{}_3\text{and SO}{}_3\text{?}\text{SO}{}_2\text{+}\text{1}\text{2}\text{O}{}_2$. Via the gaseous phase this CaO is transported to SiO₂ and reacts there to belite. Only 0.5 – 1.5%SO ₃ are dissolved in belite stabilizing its β-modification, but without increasing the hydraulic reactivity markedly.     

Selective steam reforming of aromatic hydrocarbons: IV. Steam conversion and hydroconversion of selected monoalkyl- and dialkyl-benzenes on Rh catalysts

Steam conversion and hydroconversion of a series of monoalkylbenzenes (C₆H₅R, R = C₂H₅, n-C₃H₇, i-C₃H₇, tert-C₄H₉) and of dialkylbenzenes (o- and p-xylenes) are studied at 713 K and atmospheric pressure on supported rhodium catalysts ($\text{Rh}\text{Al}{}_2\text{O}{}_3$, $\text{Rh}\text{SiO}{}_2$ and $\text{Rh}\text{TiO}{}_2$), and compared to the toluene steam dealkylation previously studied on the same catalysts. Three types of reaction, namely dealkylation (CC rupture on the side chain), dehydrogenation (on the side chain), and degradation (i.e., ring opening) account for virtually the whole product spectrum. Isomerization, transalkylation, and dehydrocyclization reactions may, in general, be discounted. In the presence of steam, the main initial product of monoalkylbenzene dealkylation is invariably benzene, but the splitting of the CC bonds in the middle or end of the side chain always increases with conversion. As a rule, the specific activities (per metal site) in dealkylation decrease with the degree of substitution in the alkyl group (primary > secondary > tertiary > quaternary carbon). On the other hand, the specific activities in ring opening remain constant for all the hydrocarbons and even for the benzene. In the presence of hydrogen, multiple CC bond splittings are invariably observed and benzene is no longer, in general, the principal initial product. The activities in ring opening are equally constant, but at a lower level than in steam conversion. These results are in overall agreement with the model of the dual active sites: sites I appear operative for dealkylation and dehydrogenation, whereas ring opening takes place at sites II with a high probability, independent of the alkyl group size. Possible adsorbed species on each type of site are described. An attempt is made to rationalize the effects of assorted selectivity-determining factors (metal particle size, support effects, selective poisons such as S and CO) in terms of electronic or geometric effects.     

Analysis of the temperature-time sequences for deactivating isothermal catalyst beds

A procedure is shown to determine the temperature-time sequences to keep the conversion at outlet of a fixed bed reactor subject to catalyst deactivati constant.The calculated sequences for different reaction systems follow the equation: t=$\text{k}{}_0$/k_0d$\text{E}\text{E}{}_{\mathrm{d}}$ exp($\text{E}{}_{\mathrm{d}}\text{RT}{}_0$/1.258×10⁵p_A^0.79{1-exp[$\text{E}{}_{\mathrm{d}}\text{R}$($\text{1}\text{T}$- $\text{1}\text{T}{}_0$)]}.From the analysis of the calculated sequences we have determined the values of the parameters of operation (space time, conversion and initial temperature) that give maximum values to the two functions which we sought to maximize, namely the time of operation and production.     

The measurement of very early hydration reactions of portland cement clinker by a thermoelectric conduction calorimeter

The heat evolved from very early hydration reactions of portland cement can be measured with the isothermal thermoelectric conduction calorimeter. The cement compounds involved in these reactions are primarily C₃A, NC₈A₃, KC₈A₃, C₄AF, $\text{C}{}_4\text{A}{}_3\text{S}$, CaSO₄, C₃S, and CaO. This paper will describe design, operation and applications of the thermoelectric conduction calorimeter.     

Non-classical free-radical polymerization: 3. Diffusion-control in degradative addition

The different kinetic features associated with polymerizations in which retardation arises through degradative transfer and degradative addition processes are considered. Reasons are given for believing that in reactions retarded by degradative transfer neglect of the interaction between ‘inactive’ radicals is justifiable, while with degradative addition this is not so. A kinetic treatment of the latter is developed in which all three termination reactions between propagating and inactive radicals are assumed to be diffusion-controlled with a single rate coefficient and equations are derived which permit from experimental data on rates of polymerization estimation of the definitive kinetic parameters $\text{k}{}_{\mathrm{p}}\text{k′}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{t}}$, $\text{k}{}_{\mathrm{pm}}\text{k′}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{t}}$ and $\text{k}{}_{\mathrm{fm}}\text{k′}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}{}_{\mathrm{t}}$ (k_p, k′_t, k_pm, k_fm are the rate coefficients of propagation, termination, reinitiation and degradative additions, respectively). The kinetic equations are satisfactorily consistent with ew experimental data on the polymerization of 1-vinylimidazole in ethanol solution at 70°C, for which there is strong evidence for the occurrence of degradative addition. A modified procedure for processing data for polymerizations with degradative transfer is put forward which is convenient for estimating the kinetic parameters and reveals in a simple manner the importance of re-initiation. It is suggested that this treatment could be generally useful in the early stages of the study of a retarded polymerization.     

Raman spectra,effective Debye parameter and magnetoresistance of graphitized cokes

The Raman intensity ratio R ($\text{I}{}_{1360}\text{I}{}_{1580}$), the effective Debye parameter B_eff and the maximum transverse magnetoresistance ($\text{Δρ}\text{ρ}\text{)}{}_{\mathrm{mx}}$ at liquid nitrogen temperature and 10 kG were measured on various cokes heat-treated at high temperatures. The observed values of R, B_eff and ($\text{Δρ}\text{ρ}\text{)}{}_{\mathrm{mx}}$ are closely related with each other and are discussed in relation to the lattice defects in the graphite layer planes. The plot of R against B_eff shows a linear relation, suggesting that both parameters are related to projections along a- and c-axes respectively of the same carbon atom displacement due to lattice defects. With decreasing B_eff, ($\text{Δρ}\text{ρ}\text{)}{}_{\mathrm{mx}}$ increases gradually but almost linearly with B_eff and then rapidly. This behavior has been interpreted by an analysis based on a simple two band model.     

Copoly(m,p-chloromethylstyrene-50% styrene): Copolymer molecular weights,fractionation and derivatization

Copolymerization of an equimolar mixture of m,p-chloromethylstyrene ($\text{M}$₁) and styrene ($\text{M}$₂) was carried out in chlorobenzene in the presence of AIBN at 80°C. Molecular weight analysis (by g.p.c.) of the resulting polymer samples was performed at various conversions. $\text{M}\text{?}{}_{\mathrm{<mtext>w</mtext>}}$, $\text{M}\text{?}{}_{\mathrm{<mtext>n</mtext>}}$, and ($\text{M}\text{?}{}_{\mathrm{<mtext>w</mtext>}}\text{M}\text{?}{}_{\mathrm{<mtext>n</mtext>}}$) value of 21 300, 13 800 and 1.54 were obtained at 8.9% conversion. At higher conversions, the value of $\text{M}\text{?}{}_{\mathrm{<mtext>w</mtext>}}$ remained effectively constant while $\text{M}\text{?}{}_{\mathrm{<mtext>n</mtext>}}$ decreased to 9200 at ca. 80% conversion, and then increased to 12 000 at about 100% conversion (16 h), and to 13 700 if the polymer solutions were maintained at 80°C for an additional 44 h. These results suggest that, although the termination step initially involves the combination of polymer radicals, at high conversions a large number of very low molecular weight, and unsaturated, polymer molecules are formed possibly by disproportionation involving polymer radicals and primary radicals. The unsaturated polymer molecules are subsequently polymerized by growing polymer radicals towards the end of the polymerization. It was noticed that further reaction occurred after complete depletion of monomer, involving radical attack on the unsaturated polymer molecules. Other reactions including chain transfer to polymer will also be important at high polymer concentrations. A copolymer of $\text{M}$₁ and $\text{M}$₂ was separated into four fractions on a preparative scale, and molecular weight analysis of the resulting polymer samples provided more evidence of the above interpretation. G.p.c. analysis of several derivatives of a copolymer of $\text{M}$₁ and $\text{M}$₂ showed that most molecular weights were much lower than that of the starting polymer. These results in some cases may reflect the chemical or dimensional changes introduced into the polymer molecules during derivatization.     

Mixtures of potassium sulphate and iron sulphate as catalysts for water vapour gasification of carbon: 3. Chemsitry of the in situ activation of the catalyst

Previously it was shown that certain mixtures of K₂SO₄ and FeSO₄ were excellent raw materials for catalytic water vapour gasification of carbon. It was suggested from the results that the iron salt catalyses the reduction of K₂SO₄ to K as the main catalyticly active species of gasification. This paper is concentrated on this activation process. Using TGA, DTA, ESCA, EPMA and visual observations of the melting behaviour after or during treatment of varying $\text{K}{}_2\text{SO}{}_4\text{FeSO}{}_4$ mixtures in H₂ and $\text{H}{}_2\text{H}{}_2\text{O}$ atmospheres it is found that elemental iron is formed in an early stage during heating up. This then catalyses the reduction of K₂SO₄ to K₂S, which is readily hydrolysed by water vapour to liquid KOH. K₂SO₄ and K₂S form an intermediate eutectic (m.p. = 610 °C), which favours wettability of the carbon surface and hydrolysis of K₂S. As well as FeSO₄ any iron salts can be used that are easily reduced to elemental iron in the gasification atmosphere. A general reaction scheme, including activation and catalytic gasification, is proposed. The activation of K₂SO₄ to catalytically active KOH can be described as follows: Fe-saltγFe3K₂SO₄ + 8Feγ3K₂S + 4Fe₂O₃Fe₂O₃ + 3H₂γ 2Fe + 3H₂OK₂S + H₂OγKHS+KOHKHS + H₂OγKOH + H₂S