Hydrodynamic properties and equilibrium rigidity of polyamidobenzimidazole molecules in dimethylacetamide and sulphuric acid

Translational diffusion, velocity sedimentation and viscometry of polyamidobenzimidazole (PABI) solutions in the range of M = (1–61) · 10³ have been investigated in N,N-dimethylacetamide (DMA) and 98% H₂SO₄. The dependences of D₀, S₀ and [η] on M were obtained. Tsvetkov-Klenin's hydrodynamic invariant was found to be $\text{A}{}_0\text{= 3.55 · 10}{}^{\mathrm{?10}}\text{erg deg}{}^{\mathrm{?1}}\text{mol}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>3</mtext>}}$. The equilibrium rigidity of PABI molecules was characterized by the length of the Kuhn segment $\text{A = 250 ± 100}\text{A}\text{?}$. The chain diameter was $\text{7 ± 4}\text{A}\text{?}$. The values of A in 98% H₂SO₄ and in an aprotic solvent, DMA, were virtually identical, implying that the rigid-chain conformation of PABI molecules in 98% H₂SO₄ is due to their geometrical structure rather than to the protonization of amide bonds. The significance of the latter evidently increases in PABI solutions in 100% H₂SO₄ in which A is 1.5 times as high. The decrease in rigidity of PABI as compared to that of poly-p-phenylene terephthalamide ($\text{A = 400 ± 100}\text{A}\text{?}$) is in reasonable agreement with the presence of imidazole rings in PABI molecules. The presence of these rings results in kinks in the PABI chain with angles of about 30° and hence, in the depature from parallelism of rotating bonds.     

Hydrodynamic properties and statistical coil dimensions of poly(o-chlorostyrene)

The theta temperature for the system poly(o-chlorostyrene)-methyl ethyl ketone has been determined as 24·5°. The samples used in the determination were prepared by radical polymerization. The dependence of intrinsic viscosity on molecular weight has been measured in methyl ethyl ketone at 24·5° and found to be $\text{η}{}_{\mathrm{\theta }}\text{= 4·68 × 10}{}^{\mathrm{?4}}\text{M}{}_{\mathrm{<mtext>w</mtext>}}{}^{\mathrm{<mtext>M1</mtext><mtext>2</mtext>}}$. The ratio 〈s₌²〉/M was found, by light scattering, to be 5·60 × 10^?18 cm². Analysis of the solution properties indicates that the Kurata-Yamakawa theory is valid in the vicinity of the Flory temperature (UCST).     

Dilute solution properties of poly(N-vinyl-3,6-dibromo carbazole)—III. Phase equilibrium studies

The phase relationships of poly(N-vinyl-3,6-dibromo carbazole) (PVK-3, 6-Br₂) were examined for four solvents, viz, o-chlorophenol, p-chloro-m-cresol, o-dichlorobenzene and bromobenzene. Upper critical solution temperatures (UCST) have been determined for solutions of PVK-3,6-Br, fractions in o-chlorophenol and p-chloro-m-cresol over the molecular weight range $\text{M}{}_{\mathrm{<mtext>w</mtext>}}\text{× 10}{}^{\mathrm{?4}}\text{= 125.0}\text{to}\text{4.8}$. The Flory temperature, θ, obtained from UCST for the PVK-3,6-Br₂/o-chlorophenol and PVK-3,6-Br₂/p-chloro-m-cresol systems are 66.0 and 112.9°C, respectively. The θ-temperatures were checked against molecular weight and viscosity data to determine the Mark-Houwink equations for these two theta solvents, with satisfactory agreement. The relations are

$\text{[ν] = 27.5}{}_4\text{× 10}{}^{\mathrm{?10}}\text{×}\text{M}{}^{0.50}{}_{\mathrm{<mtext>w</mtext>}}\text{(o-}\text{chlorophenol}\text{, 60.0°}\text{C}$

$\text{[ν] = 30.2}{}_4\text{× 10}{}^{\mathrm{?10}}\text{×}\text{M}{}^{0.50}{}_{\mathrm{<mtext>w</mtext>}}\text{(p-}\text{chloro}\text{-m}\text{cresol}\text{, 112.9°}\text{C}$

The characteristic ratio C_∞ = 〈R²〉₀/nl² was found to be 16.6 in o-chlorophenol at 60.0°C and 17.6 in p-chloro-m-cresol at 112.9°C. The value of the characteristic ratio C_∞ of PVK-3,6-Br₂ is of the same order of that for poly(N-vinyl carbazole). This indicates that the bromine atoms at the 3 and 6 (meta) positions have only an inappreciable effect on the hindering potential for rotation about the CC bond. This agreement of C_∞ for both polymers may also be taken as indicating that the effect of interaction between polar groups at the m-position on the hindering potential for rotation is small. The phase diagrams of PVK-3,6-Br₂ obtained in o-dichlorobenzene and bromobenzene seem to be characteristic of organized phase structures such as those found in systems exhibiting thermoreversible gelation. Light scattering measurement on PVK-3,6-Br₂ dissolved in o-dichlorobenzene, a gelation promoting solvent, and tetrahydrofuran, a very good solvent, strongly indicate that the macromolecular species in o-dichlorobenzene contain some extent supermolecular structures (aggregates, association of chain segments, etc.). These characteristic structures of PVK-3,6-Br₂ in o-dichlorobenzene and bromobenzene at 25°C are also characterized by high values of the Huggins' constant k′; for tetrahydrofuran solutions, the k′ values were in the range normally found for many good solvent-polymer systems.     

Intramolecular relaxation of polystyrene in a theta solvent by photon-correlation spectroscopy

Photon-correlation spectroscopy has been used to measure the diffusion coefficient D and first-mode intramolecular relaxation time τ₁ of polystyrene in a theta solvent, cyclohexane at 34.5°C. Measurements were made on five narrow fractions ($\text{M}$_w = 2.88 × 10⁶ to 9.35 × 10⁶) as a function of concentration c, in the dilute regime. D varied linearly with c, D = D_o (I + k_Dc), with D_o = (1.4 ± 0.2) × 10^?4$\text{M}{}_{\mathrm{w}}{}^{\mathrm{?(0.508\pm 0.007)}}$ cm² s^?1. Although the values obtained for τ₁ were reproducible to within 5%, no systematic variation with c was detected. The results are fitted by the relation τ₁ = (7.7 ? 0.3) × 10^?8$\text{M}{}_{\mathrm{w}}{}^{\mathrm{(1.42\pm 0.05)}}$ μs, which agrees well with the theoretical expression of Zimm for the non-draining bead-and-spring model, modified for the light-scattering case.     

NMR study of hydrogen molybdenum bronzes: H1.71MoO3 and H0.36MoO3

Proton NMR relaxation times (T₂T₁, and T_1?) and absorption spectra are reported for the compounds H_1.71MoO₃ (red monoclinic) and H_0.36MoO₃ (blue orthorhombic) in the temperature range 77 K < T < 450 K. Rigid lattice dipolar spectra show that both compounds contain proton pairs, as OH₂ groups coordinated to Mo atoms in H_1.71MoO₃ and as pairs of OH groups in H_0.36MoO₃. The room temperature lineshape for H_1.71MoO₃ shows that the average chemical shielding tensor has a total anisotropy of 20.1 ppm. The relaxation measurements confirm that hydrogen diffusion occurs and give E_A = 22 kJ mole^?1 and $\text{τ}{}^0{}_{\mathrm{<mtext>C</mtext>}}\text{? 10}{}^{\mathrm{?13}}\text{sec}$ for H_1.71MoO₃ and E_A = 11 kJ mole^?1 and $\text{τ}{}^0{}_{\mathrm{<mtext>C</mtext>}}\text{? 3 × 10}{}^{\mathrm{?8}}\text{sec}$ for H_0.36MoO₃.     

Mutual solubility of n-butanol + water under high pressures

The mutual solubilities of {xCH₃CH₂CH₂CH₂OH+(1-x)H₂O} have been determined over the temperature range 302.95 to 397.75 K at pressures up to 2450 atm. An increase in temperature and pressure results in a contraction of the immiscibility region. The results obtained for the critical solution properties are: T_o(U.C.S.T.) = 397.85 K and x_o = 0.110 at 1 atm; $\text{(}\text{dT}{}_{\mathrm{o}}\text{d}\text{p}\text{) = ?(12.0±0.5)×10}{}^{\mathrm{?3}}\text{K atm}{}^{\mathrm{?1}}$ at p < 400 atm and $\text{(}\text{dT}{}_{\mathrm{o}}\text{d}\text{p}\text{) = ?(7.0±0.7)×10}{}^{\mathrm{?3}}\text{K atm}{}^{\mathrm{?1}}$ at 800 atm < p < 2500 atm; $\text{(}\text{dx}{}_{\mathrm{o}}\text{d}\text{T}\text{) = ?(4.0±0.5)×10}{}^{\mathrm{?4}}\text{K}{}^{\mathrm{?1}}$.     

Synthesis of homoleptic tris(organo-chelate)iridium(III) complexes by spontaneous ortho-metallation of electronrich olefin-derived N,N′-diarylcarbene ligands and the X-ray structures of fac-[Ir{CN(C6H4Me-p) (CH2)2NC6H3Me-p}3] and mer-Ir{CN(C6H4Me-p)(CH2)2NC6H3Me-p}2 {CN(C6H4Me-p)(CH2)2NC6H4Me-p}Cl (a product of HCl cleavage)

Treatment of [{Ir(COD)(μ-Cl)}₂] with excess of the electron-rich olefin [$\text{CN(Ar)(CH}{}_2\text{)}{}_2\text{N}$Ar]₂ (abbreviated as (L^Ar)₂, Ar = C₆H₄Me-p or C₆H₄OMe-p) affords the ortho-metallated tricycle [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₃], which for Ar = C₆H₄Me-p (Ia) with HCL yields [$\text{Ir(L}{}^{\mathrm{A}}\text{r}$)₂(L^Ar)]Cl (IV); X-ray data show that in IV there is an unexpectedly close Ir?C(o-aryl) contact (2;52(1) Å) involving the “free” L^Ar which compares with an IrC(o-aryl) distance of 2.09(3) Å in Ia or 2.07(3) Å in the ortho-metallated L^Ar ligand of complex IV.     

Etude comparative des structures type K4NiF4 et pérovskite par la méthode des invariants

The study of K₂NiF₄ and perovskite structure type by the “method of invariants” leads to the relationship: $\text{(A-X)}{}_9\text{2}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{? (A-X)}{}_{12}\text{=}\text{constant}$, where (A-X)₉ and (A-X)₁₂ are the invariant values associated with cation A in coordination number 9 and 12. In the case where A = K⁺ and X = F^?, we propose the relationship:

$\text{(K}{}^{\mathrm{+}}\text{?F)}{}_{\mathrm{R}}\text{= 2.832 R}{}^{\mathrm{<mtext>1</mtext><mtext>11.4</mtext>}}$

where R is the coordination number.     

Light-scattering of polyamide hydrazide solutions and conformational characteristics of its molecules

Light-scattering measurements have been carried out for 18 samples of polyamide hydrazide (PAH) in dimethylsulphoxide (DMS) with an over 10-fold variation in molecular weights. It was shown that the excluded volume effect in DMS does not appreciably affect the size of PAH molecules. The length of the Kuhn segment (A ≈ 240 · 10^?8 cm) was estimated from the experimental determinations of molecular weights $\text{M}{}_{\mathrm{w}}$ and the radii of gyration 〈R²〉_z. Viscometric determination of the rigidity of PAH chains yields the value of A ≈ 200 · 10^?8 cm and the hydrodynamic diameter d ≈ 5 · 10^?8 cm. The whole collection of data shows that PAH is a typical rigid-chain polymer; the extended conformation is due to the backbone rigidity tather than to the excluded volume effects.     

Unperturbed dimensions of polystyrene in mixed solvents at high temperature

At 371.5 K, which is the θ-temperature for polystyrene (PS) in 3-methyl cyclohexanol (MC), intrinsic viscosities [η] have been measured for PS samples of different relative molar mass M in mixtures of MC with a thermodynamically good solvent 1,2,3,4-tetrahydronaphthalene over the whole range of solvent composition. Eleven graphical procedures have been utilised and assessed in deriving the unperturbed polymer dimensions expressed as K_θ (in the relation $\text{[η] = K}{}_{\mathrm{\theta }}\text{M}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{α}{}^3$ where α is the expansion factor). For those procedures concluded to be the most reliable, there was no influence of binary solvent composition: the value of K_θ = 78 (±1) × 10^?3 dm³ kg^?1 was the same as that obtained directly under θ-conditions.     

Cesium chromate,Cs2CrO4: heat capacity and thermodynamic properties from 5 to 350 K

The heat capacity of a sample of Cs₂CrO₄ was determined in the temperature range 5 to 350 K by aneroid adiabatic calorimetry. The heat capacity at constant pressure C_p^o(298.15 K), the entropy S^o(298.15 K), the enthalpy {H^o(298.15 K) - H^o(0)} and the function $\text{? {G}{}^{\mathrm{o}}\text{(298.15}\text{K}\text{) - H}{}^{\mathrm{o}}\text{(0)}}\text{298.15}\text{K}$ were found to be (146.06 ± 0.15) J K^?1 mol^?1, (228.59 ± 0.23) J K^?1 mol^?1, (30161 ± 30) J mol^?1, and (127.43 ± 0.13) J K^?1 mol^?1, respectively. The heat capacity C_p^o(298.15 K) and entropy S^o(298.15 K) and entropy S^o(298.15 K) of Rb₂CrO₄ are estimated to be (146.0 ± 1.0) J K^?1 mol^?1 and (217.6 ± 3.0) J K^?1 mol^?1, respectively.     

EPR and magnetization of GdGa2

Paramagnetic resonance and magnetic measurements were performed on powdered samples of GdGa₂. The magnetic data indicated ferrimagnetic behavior with $\text{T}{}_{\mathrm{c}}\text{? 181°}\text{K}$. Above 250° K the susceptibility obeys the Curie-Weiss law $\text{χ}{}_{\mathrm{g}}\text{=}\text{2.66}{}_2\text{× 10}{}^{\mathrm{?2}}\text{(T ? 27.6)}\text{emu/g-Oe}$ which corresponds to an effective moment of 7.95 Bohr magnetons. Over the range from 190 to 300°K the data obey a Néel type law, $\text{χ}{}_{\mathrm{g}}{}^{\mathrm{?1}}\text{= 35.95 (T ? 12.5) ?}\text{2.20 × 10}{}^4\text{(T ? 177)}$, which is indicative of ferrimagnetic order. The resonance measurements were performed at 9.013 gHz at 247, 296, and 349°K. The spectra were analyzed with a computerized curve-fitting technique that involves a linear combination of Lorentzian absorption and dispersion susceptibility components. Following demagnetization corrections, the g-factor was found to be 1.983₂ while the half-power, half-linewidth was 592.7 Oersteds.     

Kinetics and mechanism of the interaction of hexaaquochromium(III) with octacyanomolybdate(IV) ions

The kinetics of the interaction of hexaaquochromium(III) ion with potassium octacyanomolybdate(IV) have been studied using conductance and spectrophotometric data. The mechanism of the reaction is discussed and the effect of H⁺ ion and the ionic strength on the rate of the reaction determined. The reaction is found to be pseudo-first order with respect to potassium octacyanomolybdate(IV) and inverse first order with [H₃O⁺]. The rate of the reaction increases with increase in ionic strength and temperature. Activation parameters have been calculated using the Arrhenius equation and have the values ΔE^* = 1.3 × 10² kJ mol^?1, ΔH^* = 129 kJ mol^?1, ΔS^* = ?315 e.u., ΔF^* = 2.3 × 10² kJ and A = 1.5 × 10^?3. The mechanism proposed is based on ion-pair formation and the rate equation obtained is given by: k_obs=$\text{[}{}_{\mathrm{kK}}{}_{\mathrm{<mtext>E</mtext>}}\text{[H}{}_3\text{O}{}^{\mathrm{+}}\text{]+}\text{k′K′k}{}_{\mathrm{E}}\text{k}{}_{\mathrm{h}}\text{][Mo(CN)}{}_8{}^{\mathrm{4?}}\text{]}\text{[H}{}_3\text{O}{}^{\mathrm{+}}\text{]+}\text{k}{}_{\mathrm{<mtext>h</mtext>}}\text{+[}\text{K}{}_{\mathrm{<mtext>E</mtext>}}\text{[H}{}_3\text{O}{}^{\mathrm{+}}\text{]+}\text{K′}{}_{\mathrm{E}}\text{k}{}_{\mathrm{h}}\text{][Mo(CN)}{}_8{}^{\mathrm{4?}}\text{]}$     

Dilute solution properties of polylaurolactam

For a number of fractions and unfractionated samples of polylaurolactam, molecular weights ($\text{M}{}_{\mathrm{<mtext>w</mtext>}}\text{= 1 × 10}{}^4\text{?12·5 × 10}{}^4$) were measured by the light-scattering method in a mixed solvent of m-cresol with 60 vol. % 2,2,3,3-tetrafluoropropanol; intrinsic viscosities were determined in m-cresol and 96% H₂SO₄, and the constants of the Mark-Houwink equation were calculated. The calculated values of the characteristic ratio of unperturbed dimensions (virtually identical for m-cresol and 96% H₂SO₄) were compared with the respective values for polypyrrolidone and polycaprolactam. It was found that the higher frequency of the CONH-groups reduces the rigidity of the polyamide chain.     

Persulphate initiated polymerisation of methacrylamide—I: Kinetics and molecular weight dependences

A kinetic study of the aqueous persulphate initiated polymerisation of methacrylamide has shown that the rate of polymerisation is represented by the equation $\text{R}{}_{\mathrm{p}}\text{= k [}\text{M}\text{] [}\text{I}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ where the overall rate constant, $\text{k = 1.3 × 10}{}^9\text{exp}\text{(?18,400/}\text{RT}\text{) 1}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{mol}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}\text{s}{}^{\mathrm{?1}}$. Chain transfer with monomer, where C_M = 5.4 × 10^?3 at 60°, is shown to be the dominant transfer step. Comparison with kinetic studies of the analogous acrylamide polymerisation shed doubt on the ‘cage effect’ interpretation of complex orders with respect to monomer. An alternative explanation is proposed.     

Study of copper-chromium oxide catalyst: I. Thermal decomposition of copper(III) chromate,CuCrO4

The kinetics, mechanism, and activation energy of the isothermal decomposition of CuCrO₄ was studied using an isothermal TG method and an X-ray high-temperature diffraction technique in either air or a flowing atmosphere of N₂. The enthalpy change ΔH of the decomposition reaction

$\text{2}\text{CuCrO}{}_4\text{→}\text{CuO}\text{+}\text{CuO}\text{+}\text{CuCr}{}_2\text{O}{}_4\text{+}\text{3}\text{2}\text{O}{}_2$

was determined by DSC analysis. The mechanism of the thermal decomposition of CuCrO₄ is well represented by the standard Avrami-Erofeev kinetic equation $\text{[?}\text{ln}\text{(1 ? α)]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{= kt}$. According to this mechanism, the reaction rate is controlled by the formation and growth of nuclei on the surface of the reactant. The activation energy E_A of the process in air is E_A = (248 ± 8) kJ mole^?1, in flowing atmosphere of nitrogen E_A = (229 ± 8) kJ mole^?1. ΔH in air is 110 kJ mole^?1, in flowing nitrogen 67 kJ mole^?1. The lower values of ΔH and E_A in the flowing atmosphere of nitrogen are due to the fast elimination of O₂ from the reaction interface. However, the decay of the crystalline portion of CuCrO₄ during its thermal decomposition, studied by the X-ray diffraction, is controlled by a different reaction mechanism (first-order kinetics). The reaction mechanism is discussed in the relation to the crystal structure of the reactants.     

A differential scanning calorimetric study of the radical polymerization of N-vinylpyrrolidone in dimethylformamide

Polymerization of N-vinylpyrrolidone (NVP) in dimethylformamide was studied by differential scanning calorimetry (DSC). The concentration of NVP was 0.75 M, that of the radical initiator (azobisisobutyronitrile) 0.01 or 0.02 M. For proper evaluation of scanning thermograms, it was necessary to correct for incomplete monomer conversion due to premature initiator exhaustion and to consider the instantaneous initiator concentration. If these points were allowed for in the computations, activation parameters agree well with those obtained from isothermal thermograms. The values for the overall activation energy were E_a = 82 and 84 kJ/mol, and those for the pre-exponential factor $\text{Z = 6 × 10}{}^{\mathrm{?9}}\text{and}\text{13 × 10}{}^{\mathrm{?9}}\text{(}\text{mol/l}\text{)}{}^{\mathrm{<mtext>?1</mtext><mtext>2</mtext>}}\text{.}\text{sec}{}^{\mathrm{?1}}$, obtained from the scanning (dynamic) and the isothermal method, respectively.     

Effects of tris (phenanthroline)-iron(III) complex on the polymerization of styrene

The polymerization of styrene initiated by 2,2′ azobisisobutyronitrile had been studied in N,N-dimethylformamide at 60°, in the presence of Tris(phenanthroline)-iron(III) perchlorate. The complex was prepared in situ by mixing phenanthroline with hexakis (N,N-dimethylformamide) iron(III) perchlorate in the ratio 3:1. The nature of the complex formed was established by Job's method. The equilibrium constant for

$\text{Fe}{}^{\mathrm{3+}}\text{+ 3}\text{Phen}\text{? [}\text{Fe(Phen)}{}_3\text{]}{}^{\mathrm{3+}}$

is 2·3 × 10² 1³ mol^?3. The velocity constant at 60° for the reaction of polystyryl radical with [Fe(Phen)₃]³⁺ is 2·93 × 10⁴ mol^?1 l s^?1.     

Determination of the molecular weight of polyacrylamide fractions by osmometry

The polymerization of acrylamide, initiated with permanganate/oxalic acid, has been studied at 35 ± 0.2 in an aqueous medium under nitrogen. Samples of polyacrylamide were fractionated by the triangular fractionation method using methanol as non-solvent. Molecular weights of the fractions have been determined by viscometry and osmometry. Integral and differential distribution curves were plotted using the fractionation data. The narrow molecular weight distribution for high conversion polymers has been discussed. For fractionated samples of polyacrylamide in water at 30°, the equation $\text{[η]}{}_{\mathrm{ml/g}}\text{= 6.5 × 10}{}^{\mathrm{?3}}\text{M}{}_{\mathrm{n}}{}^{0.82}$ is applicable for the molecular weight range 4 × 10⁴ to 127 × 10⁴. This equation is very similar to the equation $\text{[η]}{}_{\mathrm{ml/g}}\text{= 6.31 × 10}{}^{\mathrm{?3}}\text{M}{}_{\mathrm{/}}{}^{0.80}$ of Scholtan. Other parameters (osmotic second virial coefficient and unperturbed dimension) have also been evaluated.     

Tracer diffusion coefficient of oxide ions in LaCoO3 single crystal

The tracer diffusion coefficient, $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$, of oxide ions in LaCoO₃ single crystal was determined over the temperature range of 700–1000°C by a gas-solid isotopic exchange technique using ¹⁸O tracer. For the determination, two methods, the gas phase analysis and the depth profile measurement, were employed. Under an oxygen pressure of 34 Torr, the temperature dependence of $\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$ in LaCoO₃ was expressed by

$\text{D1}{}_{\mathrm{<mtext>O</mtext>}}\text{(}\text{cm}{}^2\text{·}\text{sec}{}^{\mathrm{?1}}\text{) = 3.63 × 10}{}^4\text{exp}\text{?}\text{(74 ± 5)}\text{kcal}\text{·}\text{mole}{}^{\mathrm{?1}}\text{RT}$

$\text{D1}{}_{\mathrm{<mtext>O</mtext>}}$ at 950°C was found to be proportional to P^?0.35_O2. The diffusion of oxide ions occurs through a vacancy mechanism. The activation energy for the migration of oxide ion vacancies was estimated as 18 kcal · mole^?1.