Measurements of excess molar enthalpy and excess molar heat capacity of (1-heptanol or 1-octanol)+(diethylamine or <Emphasis Type="Italic">s</Emphasis>-butylamine) mixtures at 298.15 K and 0.1 MPa

Experimental data of excess molar enthalpy (H _m^E) and excess molar heat capacity (C _pm^E) of binary mixtures containing (1-heptanol or 1-octanol)+(diethylamine or s-butylamine) have been determined as a function of composition at 298.15 K and at 0.1 MPa using a modified 1455 Parr solution calorimeter. The excess molar enthalpy data are negative and show parabolic format over the whole composition range; however, the excess molar heat capacity values, whose curves show a S-shape, are positive in the 0.0 to 0.7 molar fraction range and negative between the molar fraction values 0.7 to 1.0. The applicability of the ERAS-model to correlate the excess molar enthalpy data was tested. The calculated data values are in good agreement with the experimental ones. The experimental behavior of H _m^E is interpreted in terms of specific interactions between 1-alkanol and amine molecules.     

Automatic initialisation of buffer composition estimation for on-line analysis of unknown buffer solutions

An automatic initialisation procedure for extracting useful information about buffer composition from a titration experiment is presented in this paper. The initialisation procedure identifies which buffering components are present in the sample from a relatively long list of buffers expected in the system monitored. The procedure determines approximate pK _a values of the buffers and evaluates their maximum and minimum concentrations. This information is then used to start an optimisation procedure to fit the model of the buffer components to the titration data and to accurately determine buffer concentrations and pK _a values. The procedure has been integrated as a software layer around the buffer capacity optimum model builder (BOMB) that fits a buffer-capacity model to a measured buffer-capacity curve to estimate model properties (pK _a values and concentrations). The reliability and robustness of the resulting buffer capacity software (BCS) were tested using a titrimetric analyser simulator (TAS). The BCS was then validated off-line and on-line.     

Characteristic length of the glass transition

The definition of molecular cooperativity is discussed. The characteristic length of the glass transition describes the size of this cooperativity. Differential scanning calorimetry (DSC) and heat capacity spectroscopy (HCS) results of a series of poly(n-alkyl methacrylates) (alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl) and a series of statistical copolymers poly(n-butylmethacrylate-stat-styrene) are discussed in terms of molecular cooperativity in the αβ splitting region, where a high-frequency dispersion zone a splits off into the main transition zone α and a Goldstein Johari process β at lower frequencies. The characteristic length tends to small values of order one monomer diameter in the splitting region for scenarios with an α relaxation onset. The statements about the size scale of cooperativity are conditional upon certain assumptions leading to the equation used for calculation of this size from HCS and DSC data. The step height of heat capacity (Δc_p) and, with less certainty, the square root of the cooperativity volume or number (V^1/2_α or ^1/2_α) are proportional to the temperature distance from the cooperativity onset, T = T_ons. © 1996 John Wiley & Sons, Inc.     

Dilute solution properties of styrene–acrylonitrile and styrene–methyl methacrylate copolymers. II. Short-range and long-range interactions from intrinsic viscosity data

Experimental data on styrene–acrylonitrile (St–AN), and styrene–methyl methacrylate (St–MMA) copolymers reported in Part I of this series are tested by “two-parameter” theoretical relations. The Fox–Flory (F–F) parameter K is estimated using the F–F, Stockmayer–Fixman (S–F), and Inagaki–Ptitsyn (I–P) equations. In general, the K values obtained by the F–F equation are low for the three St–AN copolymer samples in the systems studied while the values obtained from S–F and I–P equations agree within the limits of experimental error. Values of K obtained from Kurata–Stockmayer (K–S) equation for sample SA₁ agree with values obtained by the S–F and I–P equations. The specific solvent effect on the K values is discussed. Values of the unperturbed dimension r?0²/M?_w, calculated from the K values estimated from the S–F equation and from the homopolymer data are compared. Except in one case, the calculated r?0²/M?_w values from homopolymer data are low in comparison with the values obtained from experimental data, which shows that the presence of the repulsive interactions between unlike monomer units brings about an expansion of copolymer molecule. The effect of composition on the steric factor σ values is discussed. The long-range interaction parameter B, the excess interaction parameters ΔB_AB, and χAB are calculated. The effects of composition and solvent on these parameters are discussed.     

A reassessment of some restricted Hartree–Fock limit molecular energies and an investigation of the applicability of Ermler and Kern's procedure for their estimation

New estimates of Hartree–Fock limit energies (E_RHF) for selected AH and AH_n hydrides, diatomic and linear polyatomic molecules have been made utilizing E_SCF values recently reported in the literature for HF, N₂, CO, NH₃, and CH₄ which are very close to the respective limits. These new values have been used to investigate the applicability of Ermler and Kern's procedure for estimating E_RHF: i.e., a factor f is first evaluated from data for reference molecules, where f = E_RHF/E_SCF, which is then used with E_SCF values for other molecules to obtain their E_RHF values. f has been evaluated for three groups of reference molecules? HF, H₂O, NH₃, CH₄, N₂, and CO; CH₄, C₂H₂, C₂H₄, and C₂H₆; and C₂H₂, HCN, and N₂? utilizing E_SCF data in the literature for many Gaussian-type orbital (GTO) basis sets together with some new values calculated at the (9,5,1) to (13,8,2) levels. Trends in the variation of f within each group of reference molecules from one basis set to another, and the trends in f from one group of reference molecules to another, are discussed in detail. To minimize the influence of these effects in an E_RHF estimate it is recommended that the f value should be derived from reference molecules which possess a similar combination of structural features, i.e., bonded hydrogen, single, double, or triple bonds, and the number of lone-pair electrons. Further calculations show that an f value based on data for closed-shell molecules is not applicable to open-shell species.     

Gas-chromatographic method of evaluation ofn-alkanol ability for self-association in pure liquid

The values of the gas-chromatographic indicator reflecting the capacity of analytes for self-association in pure liquids, δT _b.p., were estimated for C₁–C₉ and C₁₁ n-alkanols by capillary gas chromatography on a nonpolar stationary phase under isothermal conditions. The δT _b.p. values ofn-alkanols, found as the difference between the boiling points measured directly and those calculated from GC data, are correlated with thermodynamic characteristics of the formation ofn-alkanol associates in pure liquids. Usingn-alkanols as analytes with insignificant temperature increments of the retention indices, it was shown that the δT _b.p. values can be determined under conditions used in gas chromatography with temperature programming. In this way a single chromatographic run can be used to compare the capacities for self-association of analytes boiling over a wide temperature range. The C₂–C₉ n-alkanethiols, which are not associated in neat liquids, have negative δT _b.p. values. An interpretation of this finding is proposed. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 2, pp. 315–318 February, 2000.     

Measurement of thermal diffusivity and specific heat capacity of polymers by laser flash method

We measured thermal diffusivity and heat capacity of polymers by laser flash method, and the effects of measurement condition and sample size on the accuracy of the measurement are discussed. Thermal diffusivities of PTFE films with thickness 200–500 μm were the same as those data that have been reported. But, the data for film thickness less than 200 μm have to be corrected by an equation to cancel thermal resistance between sample film and graphite layers for receiving light and detecting temperature. Thermal diffusivity was almost unaffected by the size of area vertical to the direction of laser pulse, because heat flow for the direction could be negligible. Specific heat capacity of polymer film was exactly measured at room temperature, provided that low absorbed energy (< 0.3 J) and enough sample mass (> 25 mg) were satisfied as measuring conditions. Thermal diffusivity curve of PS or PC versus temperature had a terrace around T_g, whereas that of PE decreased monotonously with increasing in temperature until T_m. Further, we estimated relative specific heat capacity (RC_p) by calculating ratios of heat capacities at various temperatures to the one at 299 K. RC_p for PS obtained by laser flash method was larger than that obtained by DSC method, whereas the RC_ps for PE obtained by the both methods agreed with one another until T_m (305 K). RC_p for PS decreased linearly, with increase in temperature after it increased linearly until T_g (389 K), showing similarity to temperature dependency of thermal conductivity. RC_p for PE also decreased until T_m, similar to thermal conductivity. ©1995 John Wiley & Sons, Inc.     

Low-temperature heat capacity of diglycylglycine

Heat capacity of tripeptide diglycylglycine was measured in a temperature range from 6.5 to 304 K. The results were compared with those for glycine and glycylglycine. Peptide bonding was found not to change C _P(T) virtually above 70 K, where heat capacity does not obey the Debye model. Comparison with literature data allows one to expect a significant difference in the heat capacity for enantiomorph and racemic species of valine and leucine, like it was found recently for D-and DL-serine.     

Thermal properties of seed proteins

The sample of LiCoO₂ was synthesized, and the heat capacity was measured by adiabatic calorimetry between 13 and 300 K. The smoothed values of the heat capacity were calculated from the data. The thermodynamic functions, standard enthalpy, entropy and Gibbs energy, of LiCoO₂ were calculated from the heat capacity and the numerical values are tabulated at selected temperatures from 15 to 300 K. The heat capacity, enthalpy, entropy, and Gibbs energy at T=298.15 K are 71.57 J K^–1mol^–1, 9.853 kJ mol^–1, 52.45 J K^–1 mol^–1, –5.786 kJ mol^–1, respectively. This revised version was published online in August 2006 with corrections to the Cover Date.     

Phase Behavior in Blends of Ethylene Oxide–Propylene Oxide Copolymer and Poly(ether sulfone) Studied by Modulated-Temperature DSC and NMR Relaxometry

The state diagram of a blend consisting of a copolymer containing ethylene oxide and propylene oxide, P(EO-ran-PO), and poly(ether sulfone), PES, is constructed by using modulated-temperature differential scanning calorimetry (MTDSC), T₂ NMR relaxometry, and light scattering. The apparent heat capacity signal in MTDSC is used for the characterization of polymer miscibility and morphology development. T₂ NMR relaxometry is used to detect the onset of phase separation, which is in good agreement with the onset of phase separation in the apparent heat capacity from MTDSC and the cloud-point temperature as determined from light scattering. The coexistence curve can be constructed from T₂ values at various temperatures by using a few blends with well-chosen compositions. These T₂ values also allow the detection of the boundary between the demixing zones with and without interference of partial vitrification and are in good agreement with stepwise quasi-isothermal MTDSC heat capacity measurements. Important interphases are detected in the heterogeneous P(EO-ran-PO)/PES blends.     

Thermodynamic properties of α-platinum dichloride

The heat capacity of crystalline α-platinum dichloride was measured for the first time in the temperature intervals from 11 to 300 K (vacuum adiabatic microcalorimeter) and from 300 to 620 K (differential scanning calorimetry). In the 300–620 K temperature interval, the C° _p values for α-PtCl₂ (cr) coincide with the heat capacity of CrCl₂ (cr) within the limits of experimental error, which made it possible to estimate the heat capacity of α-PtCl₂ (cr) at higher temperatures. The approximating equation of the temperature dependence of the heat capacity in the interval from 298 to 900 K C° _p (±0.8) = 63.5 + 21.4·10⁻³ T + 0.883·10⁵/T ² (J mol⁻¹ K⁻¹) was derived using the experimental values, as well as the literature data on the heat capacity of CrCl₂ (cr). For the standard conditions, the C° _p,298.15 and S°_298.15 values are 70.92±0.08 and 100.9±0.33 J mol⁻¹ K, respectively; H°_298.15 − H°₀ = 14 120±42 J mol⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1136–1138, June, 2008.     

Effects of Adsorption Mechanisms on the Efficiency of ASC Whetlerite Carbon Reactor

Dynamic adsorption equation was evaluated for its validity to characterize two different initial adsorption mechanisms with dimethyl methylphosphonate (DMMP) and cyanogen chloride (CNCl) onto ASC whetlerite carbon. Experimental results show that a linear relation between breakthrough time and the amount of carbon was occurred with high values of coefficient of correlation (0.9790–0.9993 for DMMP, 0.9979–0.9998 for CNCl) satisfying the pre-requirement for application of the adsorption equation. With initial adsorption data, as superficial flow rate increases, the dynamic adsorption capacity for DMMP increases and that for CNCl decreases which are not consistent with the earlier observation of less-relationship between dynamic adsorption and superficial flow rate. An effort was conducted to obtain numerical formulas for the dynamic adsorption capacity as a function of superficial flow rate and the calculated maximum adsorption capacities for DMMP and CNCl were 0.4291 (g/g) and 0.2500 (g/g), respectively.For DMMP, W_e = 0.3328{ 1 - exp( - 0.0626V_f )} + 0.0936W_e = 0.3328\{ 1 - \exp ( - 0.0626V_f )\} + 0.0936     

A Branched Pore Model Analysis for the Adsorption of Acid Dyes on Activated Carbon

A new branched-pore adsorption model has been developed using an external mass transfer coefficient, K _f, an effective diffusivity, D _eff, a lumped micropore diffusion rate parameter, K _b, and the fraction of macropores, f, to describe sorption kinetic data from initial adsorbent-adsorbate contact to the long-term adsorption phase. This model has been applied to an environmental pollution problem—the removal of two dyes, Acid Blue 80 (AB80) and Acid Red 114 (AR114), by sorption on activated carbon. A computer program has been used to generate theoretical concentration-time curves and the four mass transfer kinetic parameters adjusted so that the model achieves a close fit to the experimental data. The best fit values of the parameters have been determined for different initial dye concentrations and carbon masses. Since the model is specifically applicable to fixed constant values of these four parameters, a further and key application of this project is to see if single constant values of these parameters can be used to describe all the experimental concentration-time decay curves for one dye-carbon system.The error analysis and best fit approach to modeling the decay curves for both dye systems show that the correlation between experimental and theoretical data is good for the fixed values of the four fitted parameters. A significantly better fit of the model predictions is obtained when K _f, K _b and f are maintained constant but D _eff is varied. This indicates that the surface diffusivity may vary as a function of surface coverage.     

Thermodynamic properties of some N-alkyl-N-methylpiperidinium chlorides and N-alkylpiperidine hydrochlorides in water

Densities and heat capacities at 25°C were measured for N-octyl-, N-decyl- and N-dodecyl-N-methylpiperidinium chlorides and for N-octyl- and N-dodecylpiperidine hydrochlorides in water as functions of concentration. Enthalpies of dilution at 25°C and osmotic coefficients at 37°C of the N-methyl-N-alkylpiperidinium chlorides were also measured as functions of concentration. The partial molar volumes, heat capacities, relative enthalpies, nonideal Gibbs energies and entropies at 25°C were derived as functions of the surfactant concentration. By increasing the alkyl chain length of the surfactant, both the apparent molar volume vs. concentration curves are shifted toward greater values while the corresponding ones for the heat capacity are moved toward more negative values. These results are consistent with the higher hydrophobicity the longer the alkyl chain of the surfactant is. In the micellar region, the entropy and enthalpy vs. log m/m _cmc curves increase in a parallel manner by decreasing the alkyl chain length of the surfactant. Consequently, the negligible effect of the hydrophobicity of the surfactant on the Gibbs energy vs. log m/m _cmc trends is due to the enthalpy-entropy compensative effect. The thermodynamic functions of micellization were graphically evaluated on the basis of the pseudo-phase transition model. The absolute values of both the volume and heat capacity of micellization increase with an increasing number of carbon atoms in the alkyl chain (n _c ). The enthalpy and entropy of micellization vs. n _c are convex curves. Comparisons are also made between the present data and those of some alkylpyridinium chlorides reported elsewhere.     

Single crystal EPR study of VO(II)-doped magnesium potassium Tutton’s salt — Part 4

Single crystal EPR studies of VO(II)-doped magnesium potassium Tutton’s salt have been carried out at room temperature. The results indicate that the paramagnetic impurity has entered the lattice, both substitutionally and interstitially and the maximum hyperfine for the substitutional site along the a axis corresponds to the minimum hyperfine for interstitial site and vice versa. The spin Hamiltonian parameters obtained from single crystal data for these sites are: Site 1, g_||=1.954(1); g=1.998(1), A_||=19.80(2) mT; A=7.61(2) mT; Site 2, g_||=1.997(1); g=1.952(1), A_||=7.66(2) mT; A=19.85(2) mT. Superhyperfine from ligand protons have been observed at certain orientations for Site 2 impurity. Powder spectrum shows a set of eight parallel and perpendicular features indicating the presence of only one site and these values matched with Site 1 values. From these observations, it has been concluded that the two vanadyl impurities are approximately at right angles to each other. Cooling the sample to 77 K does not change the spectra appreciably. The admixture coefficients have been calculated from Site 1 data, which agree well with the reported values.     

Calculation on ion exchange capacity for an ion exchanger using the potentiometric titration

We calculated the characteristics of a phosphoric cation exchanger and studied an accurately computable method for ion exchange capacity for a type of potentiometric titration curve. The ion exchanger was prepared by phosphorylation of a styrene‐divinylbenzene copolymer. The ion exchange capacity was 5.7 meq/g. The experimental pK values versus χ in a phosphoric cation exchanger can explain a linear equation. The ΔpK values were obtained from the slope of a linear equation. The ΔpK values were the differences of pK values between the apparent equilibrium constant at complete and zeroth neutralization of the ion exchanger. The experimental pK values at χ = 0.5 (χ:degree of neutralization of ion exchanger) showed good agreement with the theoretical data. When it was titrated with NaOH and Ba(OH)₂ solutions, a good agreement between experimental and theoretical pK values for various χ was found in all potentiometric titration curves. The potentiometric titration curve near the inflection point in the case of divalent ions was changed more sharply than that for monovalent ions. The plot of ∂pH/∂g versus g (number of moles of alkali to 1 g of ion exchanger) was fitted to the Lorenzian distribution, from which ion exchange capacity was accurately evaluated. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3181–3188, 2000     

Absorbed heat and heat of formation of dried microbial biomassstudies on the thermodynamics of microbial growth

As represented by equations in which there is a term representing the biomass, the thermodynamics of biological growth processes is difficult to study without knowing the thermodynamic properties of cellular structural fabric. Measurement of the heat capacity data required to determine the standard entropy, So _298,15 or the standard absorbed heat, (H o _298,15 -ΔHo ₀ =Θo _298,15 of biomass requires a low-temperature calorimter, and these are not present in most laboratories. Based on a previously described method for entropy, two equations are developed that enable values of the absorbed heat (Θo _298,15) and the absorbed heat of formation, (Δ _f Θo _298,15) for biomass to be calculated empirically which are accurate to within 1% with respect to the biomass substances tested. These equations depend on a previous knowledge of the atomic composition or the unit-carbon formulas of macromolecules or structural cellular fabric. This revised version was published online in July 2006 with corrections to the Cover Date.     

Intrinsic birefringence of poly(ethylene terephthalate)

In the existing literature various values are given for the intrinsic birefringence of the crystalline and the amorphous phases in poly(ethylene terephthalate) (PET). These values have either been calculated theoretically or obtained from experimental data on the basis of certain models. In this investigation, using the Samuels two-phase model which correlates sonic modulus with structural parameters, intrinsic birefringence values for the crystalline (Δn_c) and amorphous (Δn_a) phases have been determined by studying 30 PET samples prepared by heat setting to have a wide range of structures; the results are Δn_c = 0.29 and Δn_a = 0.20. These values are discussed along with others in the literature and it is concluded that in the light of the present work, the values used by many authors need reexamination.     

Measuring the Glass Transition of Thermosets by Alternating Differential Scanning Calorimetry

The glass transition temperature of thermosets is determined by alternating differential scanning calorimetry (ADSC), which is a temperature modulated DSC technique. The different values of the glass transition obtained from heat flow measurements (total and reversible) and heat capacity (modulus of the complex heat capacity) are analysed and compared with the values obtained by conventional DSC. The effect of the sample mass on the values of T_g, heat capacity and phase angle has been analysed. The effect of the thermal contact between sample and pan has been studied using samples cured directly inside the pan and disc-shaped samples of different thickness. The results obtained for the thermal properties and the phase angle are compared and analysed. The modulus of the complex heat capacity enables the determination of the dynamic glass transition, T_g, which is frequency dependent. The apparent activation energy ofthe relaxation process associated with the glass transition has been evaluated from the dependence of T_g on the period of the modulation.This revised version was published online in November 2005 with corrections to the Cover Date.     

Correlation of retention indices with van der Waals’ volumes and surface areas: Alkanes and azo compounds

Summary Van der Waals’ volumes (V _W) and surface areas (S _W) of alkanes, (E)-azoalkanes and structurally similar alkenes (R₁-X=X-R₂, X=N, CH) were calculated by a semiempirical quantum-chemical method (AM1). The calculated data are in reasonable agreement with the experimental values of Bondi and good correlations were found between the calculated data and Kovats’ retention indices (I _R). While theV _Ws of alkanes with the same carbon number are very close to one another, theS _Ws follow the scatter of theI _R values for branched alkanes. The difference in theI _R of (E)-azo compounds and the structurally similar alkenes can be explained by the difference inV _Ws.