Molecular dynamics studies on the structures of polymer electrolyte membranes and diffusion mechanism of protons and small molecules

We performed a series of molecular dynamics (MD) simulations on Nafion^® membranes containing various quantities of H₂O and CH₃OH. The simulations afforded diverse nanoscale phase-separated structures, such as clusters, channels, and cluster–channels. The calculated cluster–channel structure qualitatively agrees with the experimental results of X-ray diffraction studies. We also investigated the diffusion mechanisms for H₂O, protons, CH₃OH, H₂, and O₂ in these membranes. To reproduce the hopping transfer of protons, we employed a semi-classical MD approach using the empirical valence bond method. The estimated diffusion coefficients of H₂O and proton in the membranes significantly depended on the H₂O content, and these values showed qualitatively good agreement with the experimental results. The diffusion coefficient of proton in H₂O-rich membranes was much larger than that of H₂O, and the proton mainly formed H₅O₂⁺ complex. Furthermore, the simulation results indicate that the majority of CH₃OH permeates through the H₂O clusters, and the majority of H₂ and O₂ permeates through the hydrophobic region of the membrane.     

Energy Trapping in Dications

The energy interaction curves of a number of diatomic and polyatomic dication systems were calculated in order to study their energy-trapping properties. Generally, the ab initio complete active space multiconfiguration self-consistent field method was used in an extended valence + polarization basis set, with compact effective potentials replacing the core electrons. The diatomic dications include all ten possible binary combinations of oxygen, sulphur, selenium, and tellurium. O₂²⁺ shows the largest exothermicity, measured from equilibrium to the monocation combination asymptote, and highest barrier to dissociation. The calculated equilibrium bond length and harmonic vibrational frequency agree very well with experiment. The O₂²⁺, SO²⁺, SeO²⁺, and TeO²⁺ series show progressively decreasing exothermicities but similar barrier heights. The non-oxides, in contrast, show similar exothermicities but decreasing barriers with increasing size of the atom constituents. These trends are interpreted in terms of both valence bond curve-crossing and molecular orbital bonding models. The ozone dication, O₃²⁺, is found to have a number of low-lying singlet and triplet stationary state structures spanning near-linear to D_3h2+ symmetries. Although the calculated exothermicity is even larger than for O₂²⁺, the barrier to O₂⁺ + O⁺ dissociation is predicted to be low in each case. O₂²⁺ surrounded by six argon atoms to model an isolating environment shows increased equilibrium O–O bond length, decreased exothermicity, and increased barrier to dissociation, relative to the bare dication. O₂²⁺ flanked at each end by a perpendicularly oriented H₂ molecule in a staggered conformation is obstructed from direct conversion to the water dimer dication by a high barrier. However, [(H₂O)₂]²⁺ dissociates smoothly from equilibrium to two water monocations with a large exothermicity but a small barrier.     

Performance of yttria-stabilized zirconia fuel cell using H2–CO2 gas system and CO–O2 gas system

This paper reports the performance of an yttria-stabilized zirconia fuel cell (YSZ) using five kinds of gas systems. The final target of this research is to establish the combined fuel cell systems which can produce a H₂ fuel and circulate CO₂ gas in the production process of electric power. A large electric power was measured in the H₂–O₂ gas system and the CO–O₂ gas system at 1073 K. The formation process of O²⁻ ions in the endothermic cathodic reaction (1/2O₂+2e⁻→O²⁻) controlled the cell performance in both the gas systems. The electric power of the H₂–CO₂ gas system, which allowed to change CO₂ gas into a CO fuel (H₂+CO₂→H₂O+CO) in the cathode, was 1/31–1/11 of the maximum electric power for the H₂–O₂ gas system. This result is related to the larger endothermic energy for the formation of O²⁻ ions from CO₂ molecules at the cathode (CO₂+2e⁻→CO+O²⁻) than from O₂ molecules. The CO–H₂O gas system and the H₂–H₂O gas system was expected to produce a H₂ fuel in the cathode (CO+H₂O→H₂+CO₂, H₂+H₂O→H₂+H₂O). Although relatively high OCV values (open circuit voltage) were measured in these gas systems, no electric power was measured. At this moment, it was difficult to apply H₂O vapor as an oxidant to the cathodic reaction in a YSZ fuel cell.     

The solubility of selenate-AFt (3CaO·Al2O3·3CaSeO4·37.5H2O) and selenate-AFm (3CaO·Al2O3·CaSeO4·xH2O)

The Se(VI)-analogues of ettringite and monosulfate, selenate-AFt (3CaO·Al₂O₃·3CaSeO₄·37.5H₂O), and selenate-AFm (3CaO·Al₂O₃·CaSeO₄·xH₂O) were synthesised and characterised by bulk chemical analysis and X-ray diffraction. Their solubility products were determined from a series of batch and resuspension experiments conducted at 25 °C. For selenate-AFt suspensions, the pH varied between 11.37 and 11.61, and a solubility product, log K_so=61.29±0.60 (I=0 M), was determined for the reaction 3CaO·Al₂O₃·3CaSeO₄·37.5H₂O+12 H⁺⇔6Ca²⁺+2Al³⁺+3SeO₄²⁻+43.5H₂O. Selenate-AFm synthesis resulted in the uptake of Na, which was leached during equilibration and resuspension. For the pH range of 11.75 to 11.90, a solubility product, log K_so=73.40±0.22 (I=0 M), was determined for the reaction 3CaO·Al₂O₃·CaSeO₄·xH₂O+12 H⁺⇔4Ca²⁺+2Al³⁺+SeO₄²⁻+(x+6)H₂O. Thermodynamic modelling suggested that both selenate-AFt and selenate-AFm are stable in the cementitious matrix; and that in a cement limited in sulfate, selenate concentration may be limited by selenate-AFm to below the millimolar range above pH 12.     

The Effect of Proton Hydration in Wells-Dawson and Keggin Type Heteropolyacids on their Catalytic Activity in Gas Phase ETBE Synthesis

The influence of proton hydration in Wells-Dawson H₆P₂W₁₈O₆₂ (HP2W) and Keggin H₃PW₁₂O₄₀ (HPW) type heteropolyacids on their catalytic activity in ethyl-tert-butyl ether (ETBE) synthesis in gas phase was investigated. In the case of samples with the content of crystallisation water per one proton below 0.8 ([H₂O]/[H⁺] < 0.8), the catalytic activity related to the mass unit of the HP2W was higher than that of the HPW in accordance with the order of proton concentration in mass unit. On the other hand, the activity related to one mole of protons indicated higher activity in the HPW than in the HP2W in accordance with the order of acid strength. In the series of samples with [H₂O]/[H⁺] > 0.8 the activity was much higher for the HP2W than the HPW and maximum of both catalytic activity and ethanol sorption capacity was observed for the HP2W. The possible role of the secondary structure of the hydrates was discussed.     

Conductance and spectroscopy of protonic beta and beta″-aluminas

Five protonic beta and beta″-aluminas; viz hydrated sodium beta-alumina (1,24Na₂O·11Al₂O₃), hydronium beta-alumina (1.24H₂O·11Al₂O₃·2.6H₂O), partially dehydrated hydronium beta-alumina (1.24H₂O·11Al₂O₃·1.3H₂O), hydrogen beta-alumina (1.24H₂O·11Al₂O₃) and hydronium beta″-alumina (0.84H₂O·0.8MgO·5Al₂O₃·2.8H₂O) were examined by broad band nuclear magnetic resonance from ?196°C to 200°C. The spectra of hydronium beta-alumina and hydronium beta″-alumina are consistent with a mixed composition of H₂O, H₃O⁺ and H⁺ species in the conducting plane. Hydrogen beta-alumina and partially dehydrated hydronium beta-alumina appear to contain only relatively isolated (2.6–2.7Å) protons; no evidence of molecular water or hydronium ions is found. Water molecules intercalated into the conduction plane of sodium beta-alumina do not appear to be in rapid motion, even at 167°C, but are relatively stationary. The onset of motional narrowing in hydronium beta″-alumina occurs at ?40°C but not until +30°C in hydronium beta-alumina. This is consistent with the higher conductivity reported for hydronium beta″-alumina, 10^?3–10^?5 (ohm-cm)^?1 at 25°C, in comparison to 10^?10–10^?11 (ohm-cm)^?1 for hydronium beta-alumina at 25°C.     

Quantum Properties of the Excess Proton in Liquid Water

The classical and quantum equilibrium properties of an excess proton in bulk phase water are examined computationally with a special emphasis on the influence of an explicit quantum dynamical treatment of the nuclei on the calculated observables. The potential model used, our recently developed multistate empirical valence bond (MS-EVB) approach is described. The MS-EVB model takes into account the interaction of an exchange charge distribution of the charge-transfer complex with the polar solvent, which qualitatively changes the nature of the solvated complex. The impact and importance of the exchange term on the stability of the solvated H₅O₂⁺ (Zundel) cation relative to the H₉O₄⁺ (Eigen) cation in the liquid phase is demonstrated. Classical and quantum path-integral molecular dynamics (PIMD) simulations of an excess proton in bulk phase water reveal that quantization of the nuclear degrees of freedom results in an increased stabilization of the solvated Zundel cation relative to the Eigen cation, and that species intermediate between the two are also probable. Quantum effects lead to a significant broadening of the probability distributions used to characterize the two species, and a definite differentiation and sharp characterization of the species connected to the excess proton in liquid water is found to be difficult.     

Simple Directed Material Design Through in Situ Substitution of Proton with Cu+ Ions

A new inorganic–organic hybrid material (C₁₀H₈N₂H)₂(Mo₈O₂₆) · 2NH₄ (1) was prepared under solvothermal conditions (H₂O/ethanol), which was then used as a starting material in the synthesis of another material, (C₁₀H₈N₂Cu)₂(Mo₈O₂₆) · 2NH₄ (2). Each compound has been characterized by single-crystal X-ray diffraction, X-ray powder diffraction, elemental analysis, thermogravimetric analysis, fluorescence, FT-IR, and bond valence sum calculations. The comparative study focuses on the transformation and structural change between 1 and 2, which arises from the simple substitution of the proton in 1 with the Cu⁺ ions. The other surprising feature is that Cu⁺ ions can not only directly be used to substitute the proton of 1 but also ameliorate its photoluminescence property. It means that 1 appears to have recognizable functional protons in the solid-state structure and, hence, can very well be considered as an ideal precursor agent to design the functional materials with special architectures and photoactive properties.     

Proton Solvation and Proton Mobility

Experimental evidence for proton solvation and proton mobility is analyzed and the results are compared with recent simulations. Three factors contribute to differences in proton solvation energies: hydrogen-bond cleavage, changes in hydrogen-bond lengths, and proton derealization. These factors are estimated from experimental attributes. In dilute acidic aqueous solutions H₃O⁺ is more stable than H₅O₂⁺ by about 0.6 kcal/mol. This estimate, together with the activation energy for proton mobility, supports the 121 mechanism for proton mobility in which a protonated water monomer is transformed, by second-shell hydrogen-bond cleavage, to a protonated dimer and back to another protonated monomer.     

Reaction of Ozone with Ag(I)—Mechanistic Considerations

Ozone reacts slowly with Ag⁺ (circumneutral pH, k = (11 ± 3) × 10^?2 M^?1 s^?1). After some time, ozone decay kinetics may suddenly become faster with the concomitant formation of silver sol. As primary process, an O-transfer from O₃ to Ag(I) is suggested, whereby Ag(III) is formed [Ag⁺ + O₃ + 2 H₂O → Ag(OH)₃ + O₂ + H⁺]. This conproportionates with Ag(I), which is in large excess, leading to Ag(II) [Ag⁺ + Ag(OH)₃ ? 2 Ag(OH)⁺ + HO^?]. Further, Ag(II) reacts with ozone in a high exergonic reaction [Ag(OH)⁺ + O₃ → Ag + 2 O₂ + H⁺], where ozone acts as a reducing agent. Thereby, a single silver atom, Ag, is formed that can be oxidized by O₂ and O₃ or can aggregate to a silver sol. Aggregation slows down the rate of oxidation. When Ag⁺ is complexed by acetate ions, ozone decay and silver sol formation are speeded up by enhancing Ag(II) formation [Ag(I)acetate + O₃ → Ag(III)acetate → Ag(II) + CO₂ + ?CH₃]. In the presence of oxalate, the formed complex reacts faster with ozone than Ag⁺, and Ag(III)oxalate decarboxylates rapidly [Ag(I)oxalate + O₃ → Ag(III)oxalate → Ag⁺ + 2 CO₂]. This enhances ozone decay but prevents silver sol formation. Quantum chemical calculations have been carried out for substantiating mechanistic suggestions.     

Etude voltamperometrique de la n-acetyl l-tyrosine amide sur electrode a pate de graphite en milleux aqueux I—comportement dans les domaines de balayage superieurs a 0,5 v/enh

Graphite paste electrode allows to determine elementary processes of the electrochemical oxidation in aqueous media of an electrochemical probe such as: N-acetyl L-tyrosine amide. Mathematical analysis of voltammograms gives the following EC mechanism: R?C₆H₅OH?R?C₆H₅O^. + H⁺ + e 2 R?C₆H₅O^. → R?C₆H₅O⁺ + R?C₆H₅O^?, R?C₆H₅O^? + H⁺ → R?C₆H₅OH, R?C₆H₅O⁺ → [R?C₆H₄O]^.. + H⁺, n[R?C₆H₄O]^.. → ?[R?C₆H₄O]^?_n.     

Dual regulation of Li+ migration of Li6.4La3Zr1.4M0.6O12 (M = Sb,Ta, Nb) by bottleneck size and bond length of M−O

Bottleneck size is the minimum Li⁺ migration channel of Li₇La₃Zr₂O₁₂ (LLZO) and it greatly influences the Li⁺ conductivity. Doping different elements on the Zr site of LLZO can adjust the bottleneck size and improve the Li⁺ conductivity. However, the regulation mechanism is not clear. In this work, Li_6.4La₃Zr_1.4M_0.6O₁₂ (M = Sb, Ta, Nb) has been prepared and the bottleneck size has been adjusted by doping different pentavalent ions. The results manifest that the cell parameter and bottleneck size decrease with the rise of the radius of doped pentavalent ions. This is because larger pentavalent ion leads to larger bond length of M–O, and weaker covalent component between M⁵⁺ and O^2-, corresponding, the formal charge on the M⁵⁺ become larger, and the bond length of La–O slightly decreases due to the coulomb repulsion between La³⁺ and M⁵⁺ increase. While, the activation energy drop firstly and then rise with the rise of bottleneck size because of the migration of Li⁺ not only relate to the size of the migration channel but also to the strength of M–O covalent bonding. The bottleneck size and bond length of M–O synergistically affect the migration of Li⁺.     

Exploration of molten hydroxide electrochemistry for thermal battery applications

The electrochemistry of molten LiOH–NaOH, LiOH–KOH, and NaOH–KOH was investigated using platinum, palladium, nickel, silver, aluminum and other electrodes. The fast kinetics of the Ag⁺/Ag electrode reaction suggests its use as a reference electrode in molten hydroxides. The key equilibrium reaction in each of these melts is 2 OH^– = H₂O + O^2– where H₂O is the Lux-Flood acid (oxide ion acceptor) and O^2– is the Lux–Flood base. This reaction dictates the minimum H₂O content attainable in the melt. Extensive heating at 500 °C simply converts more of the alkali metal hydroxide into the corresponding oxide, that is, Li₂O, Na₂O or K₂O. Thermodynamic calculations suggest that Li₂O acts as a Lux–Flood acid in molten NaOH–KOH via the dissolution reaction Li₂O_(s) + 2 OH^– = 2 LiO^– + H₂O whereas Na₂O acts as a Lux–Flood base, Na₂O_(s) = 2 Na⁺ + O^2–. The dominant limiting anodic reaction on platinum in all three melts is the oxidation of OH^– to yield oxygen, that is 2 OH^– 1/2 O₂ + H₂O + 2 e^–. The limiting cathodic reaction in these melts is the reduction of water in acidic melts ([H₂O] [O^2–]) and the reduction of Na⁺ or K⁺ in basic melts. The direct reduction of OH^– to hydrogen and O^2– is thermodynamically impossible in molten hydroxides. The electrostability window for thermal battery applications in molten hydroxides at 250–300 °C is 1.5 V in acidic melts and 2.5 V in basic melts. The use of aluminum substrates could possibly extend this window to 3 V or higher. Preliminary tests of the Li–Fe (LAN) anode in molten LiOH–KOH and NaOH–KOH show that this anode is not stable in these melts at acidic conditions. The presence of superoxide ions in these acidic melts likely contributes to this instability of lithium anodes. Thermal battery development using molten hydroxides will likely require less active anode materials such as Li–Al alloys or the use of more basic melts. It is well established that sodium metal is both soluble and stable in basic NaOH–KOH melts and has been used as a reference electrode for this system.     

A novel hexagonal honeycomb K–Cr-oxalate anionic network with layers separated by a five-coordinated Cu(II)–pypn complex (pypn = N,N′-bis(2-pyridylmethyl)-1,3-propanediamine). Synthesis,characterisation, spectroscopy and crystal structure of {[KCr(C2O4)3][Cu(pypn)(H2O)](H2O)4}

A novel hexagonal-based honeycomb compound with overall formula {[KCr(C₂O₄)₃][Cu(pypn)(H₂O)](H₂O)₄} is reported in which pypn is with the tetradentate ligand (N,N′-bis(2-pyridylmethyl)-1,3-propanediamine). The [KCr(C₂O₄)₃]^2? moiety forms a hexagonal honeycomb structure, while the five-coordinated [Cu(pypn)(H₂O)]²⁺ moiety is located in between the layers, partly filling the holes in the cavities. The synthesis, X-ray crystal structure and some spectroscopic properties are presented. The coordination of Cr(III) is octahedral, with a CrO₆ chromophore, and the K⁺ ion is in a KO₆ environment (K–O distances vary from 2.36 to 2.48 ?). The [KCr(C₂O₄)₃]^2? layers have the K⁺ ions in a Λ conformation, while the Cr(III) ions in the Δ conformation. The geometry around the Cu(II) is five-coordinated with four nitrogens from the chelating pypn ligand in a plane and the apical position being occupied by the oxygen atom of the coordinating water molecule. The packing of the cationic and the anionic layers appears to be of special interest.     

Oxygen reduction on platinum electrodes in base: Theoretical study

Electrode-potential-dependent activation energies for electron transfer have been calculated using a local reaction center model and constrained variation theory for the oxygen reduction reaction on platinum in base. Results for four one-electron transfer steps are presented. For the first, O₂(ads) is predicted to be reduced to adsorbed superoxide, O₂⁻(ads), which dissociates with a low activation barrier to O(ads) + O⁻(ads). Then a proton transfer form H₂O(ads) to O⁻(ads) takes place, forming OH(ads) + OH⁻(aq). The second electron transfer reacts O(ads) with H₂O(aq) to form a second OH(ads) + OH⁻(aq). The third and fourth electron transfers react the two OH(ads) with two H₂O(aq) to form two H₂O(ads) + two OH⁻(aq). All three different surface reduction reactions are predicted to have reversible potentials in the −0.24 V(SHE) to −0.29 V(SHE) range for 0.1 M base and activation energies for the superoxide formation step are close to the experimentally observed range in 0.1 M base for the overall four-electron to water over the three low index (1 1 0) (1 0 0) and (1 1 1) surfaces: 0.38-0.49 eV at 0.35 eV respectively at 0.88 V(RHE). Predicted reversible potentials for forming O₂⁻(ads) are compared with estimates from the experimental literature. The difference between the acid mechanism, where the peroxyl radical, OOH(ads) is the first reduction intermediate, and the base mechanism, where superoxide, O₂⁻(ads) is the first reduction intermediate, is discussed.     

Hydration of dibarium silicate I. Stoicheiometry of hydration

Dibarium silicate, Ba₂SiO₄, was hydrated in two ways: in paste form at 25° using a water/solid weight ratio of 0.7:1, and in a polyethylene bottle rotated on a wheel at 5°, 25° and 50°, using a water/solid weight ratio of 9.0:1. When Ba₂SiO₄ is hydrated in paste form, the stoicheiometry of the reaction at 25° is the same as in bottle-hydration at 50°: 2BaO.SiO₂+2.2H₂O = 1.2BaO.SiO₂.1.4H₂O+0.8Ba(OH)₂. The stoicheiometry of bottle-hydration at 5° and 25° is represented by the equation: 2BaO.SiO₂+2.2H₂O = BaO.SiO.1.2H₂O+Ba(OH)₂. Barium silicate hydrate, 1.2BaO.SiO₂.1.4H₂O, is well crystallised and has a specific surface area of ? 3m²/g. The crystals are plate-like and have a tendency to form clusters. The low-baria hydrate, BaO.SiO₂.1.2H₂O, is poorly crystallised and consists of thin platelets. It has a specific surface area of ? 35m²/g. The thermal dehydration of fully hydrated barium silicate and of the barium silicate hydrates was investigated by thermogravimetric and differential thermal analysis techniques. The similarities and differences between the barium silicate hydrates obtained in the hydration of barium silicate and the calcium silicate hydrates obtained in the hydration of β-dicalcium silicate and Ca₃SiO₅ are discussed. A mechanism of hydration of barium silicate is proposed which involves solution, precipitation and crystallisation steps.     

An In Situ ESR Study of Pd/H-ZSM-5 Interaction with Different Adsorbents

In situ ESR at 120–473 K permits to monitor formation of transient paramagnetic ions/complexes (isolated Pd⁺ sites; Pd⁺/H₂O; Pd⁺/C₆H₆) upon interaction of isolated Pd²⁺ cations stabilized by the H-ZSM-5 matrix with different organic compounds and gas mixtures (NO, O₂, H₂O, H₂, propene, benzene). The in situ study provides insight into the elementary steps of redox processes on isolated Pd species in H-ZSM-5 zeolite under realistic conditions. Adsorbed water stabilizes the transient paramagnetic complex and decreases the rate of Pd²⁺ to Pd⁰ reduction by H₂. Strong bonding of NO _x ligands to Pd²⁺ species suppresses the reduction of Pd(II) ions. Sorption of benzene on preoxidized Pd²⁺/HZSM-5 is accompanied by an easy formation of organic cation-radicals and of a Pd⁺/benzene complex, the paramagnetic Pd⁺/benzene structure indicating a surprisingly high resistance to further reduction to Pd⁰. Illumination of the Pd/HZSM-5 by UV-visible light causes no measurable change in the redox properties of the catalyst.     

The mechanism of electrodeposition of acrylic resin on aluminium

A mechanism for the electrodeposition of acrylic resin on aluminium is proposed, based on experimental studies of acid value, anodic gas evaluation and anodic film resistance. The mechanism can be expressed as Alf Al³⁺ + 3e 2Al³⁺ + 3H₂Of Al₂O₃ + 6H⁺ 2Al³⁺ + 6H₂Of 2Al(OH)₃ + 6H⁺ H⁺ + RCOC^– f RCOOH. This is different from the mechanism for zinc and steel, where it is metal ions from anodic dissolution which neutralize the macro-ions and cause a deposit on the anode surface.     

Ion-cyclotron resonance study of elementary stages of the catalytic oxidation of CO by N2O in the presence of VIA-group metal ions

Gas phase reactions of Mo⁺ and W⁺ ions with the molecules of various oxidants (NO, O₂, N₂O, CH₂O, C₂H₄O) were studied using ion cyclotron resonance. In oxidation with N₂O the mono-, di- and trioxide metal cations are formed consecutively. The trioxide MO₃ ⁺ ions of both metals react with CO to form CO₂ and MO₂ ⁺ ions. In this way, catalytic reaction N₂O + CO N₂ + CO₂ occurs in the gas phase with MoO₃ ⁺ /MoO₂ ⁺ and WO₃ ⁺/WO₂ ⁺ couples as catalysts. The rate constants have been measured for both stages of the catalytic cycle as well as for the stages of the catalyst preparation. Metal-oxygen bond energies were estimated for MoO_x ⁺ and WO_x ⁺ species with various x. The mechanism of CO oxidation with MoO_x ⁺ and WO_x ⁺ cations as catalysts in the gas phase is discussed in comparison with that for the oxidation over classical solid oxide catalysts.     

Polymerization of allyl methacrylate with wool fabric using different initiators

Polymerization of allyl methacrylate (AMA) with wool fabrics using different initiators, namely, potassium persulphate, Fe²⁺? H₂O₂, benzoyl peroxide, ceric ammonium nitrate, and vanadium pentanitrate, was investigated. The percent of polymer add-on depends upon the type and concentration of the initiator. Addition of metallic salts such as Fe³⁺ to the polymerization system enhances polymerization significantly when benzoyl peroxide and potassium persulphate are used independently as initiator. The opposite holds true for ceric ammonium nitrate and vanadium pentanitrate. With Fe²⁺? H₂O₂, on the other hand, the enhancement is marginal. Also studied was the incorporation of Li⁺, Cu⁺⁺, and Fe³⁺ at different concentrations in AMA—wool–benzoyl peroxide polymerization systems. Determination of the polymer add-on on the basis of double bond analysis revealed that the remained double bond is governed by the magnitude of the polymer add-on as well as by the type of initiator.