Investigation of N<Subscript>2</Subscript>-fixation on polyaniline electrodes in methanol by electrochemical impedance spectroscopy

The ac response of polyaniline thin films on platinum electrodes was measured at different dc potentials during the N₂-fixation in methanol + LiClO₄ electrolyte with 0.03 mol L⁻¹ H₂SO₄ for the first time. The optimum film thickness was found to be 1.5 μm, N₂-pressure 50 bar and an optimum electrolysis potential of −0.12 V (NHE). The diffusion coefficients for N₂ into the polymer film was found to be (5 ± 2)×10⁻⁹ cm² s⁻¹.     

Chemical and electrochemical characterization of TiO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> atomic layer depositions on AZ-31 magnesium alloy

In this study, innovative TiO₂/Al₂O₃ mono/multilayers were applied by atomic layer depositions (ALD) on ASTM-AZ-31 magnesium/aluminum alloy to enhance its well-known scarce corrosion resistance. Four different configurations of ALD layers were tested: single TiO₂ layer, single Al₂O₃ layer, Al₂O₃/TiO₂ bilayer and Al₂O₃/TiO₂/Al₂O₃/TiO₂ multilayer deposited using Al[(CH₃)]₃ (trimethylaluminum, TMA), and TiCl₄ and H₂O precursors. All depositions were performed at 120°C to obtain an amorphous-like structure of both oxide layers. The four coatings were then investigated using different techniques, such as scanning electron microscope (SEM), stylus profilometer, glow discharge optical emission spectrometry (GDOES) and polarization curves in 0.05-M NaCl solution. The thickness of all the coatings was around 100 nm. The layers compositions were successfully investigated by the GDOES technique, although obtained data seem to be affected by substrate roughness and differences in sputtering rates between ceramic oxides and metallic magnesium alloy. Corrosion resistance showed to be strongly enhanced by the nanometric coatings, giving lower corrosion current densities in 0.05-M NaCl media with respect to the uncoated substrate (from 10⁻⁴ to 10⁻⁶ A/cm² for the single layers and from 10⁻⁴ to 10⁻⁸ A/cm² for the bi- and multilayers). All polarization curves on coated samples also showed a passive region, wider for the bi-layer (from −0.58 to −0.43 V with respect to Ag/AgCl) and multilayer (from −0.53 to −0.38 V with respect to Ag/AgCl) structures.     

Electrochemical oxidation of an acid dye by active chlorine generated using Ti/Sn<Subscript>(1−<Emphasis Type="Italic">x</Emphasis>)</Subscript>Ir<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> electrodes

The generation of active chlorine on Ti/Sn_(1−x)Ir _x O₂ anodes, with different compositions of Ir (x = 0.01, 0.05, 0.10 and 0.30 ), was investigated by controlled current density electrolysis. Using a low concentration of chloride ions (0.05 mol L⁻¹) and a low current density (5 mA cm⁻²) it was possible to produce up to 60 mg L⁻¹ of active chlorine on a Ti/Sn_0.99Ir_0.01O₂ anode. The feasibility of the discoloration of a textile acid azo dye, acid red 29 dye (C.I. 16570), was also investigated with in situ electrogenerated active chlorine on Ti/Sn_(1−x)Ir _x O₂ anodes. The best conditions for 100% discoloration and maximum degradation (70% TOC reduction) were found to be: NaCl pH 4, 25 mA cm⁻² and 6 h of electrolysis. It is suggested that active chlorine generation and/or powerful oxidants such as chlorine radicals and hydroxyl radicals are responsible for promoting faster dye degradation. Rate constants calculated from color decay versus time reveal a zero order reaction at dye concentrations up to 1.0 × 10⁻⁴ mol L⁻¹. Effects of other electrolytes, dye concentration and applied density currents also have been investigated and are discussed.     

Study of electrochemical properties and the charge/discharge mechanism for Li<Subscript>4</Subscript>Mn<Subscript>5</Subscript>O<Subscript>12</Subscript>/MnO<Subscript>2</Subscript>-AC hybrid supercapacitor

Spinel Li₄Mn₅O₁₂ was prepared by a sol–gel method. The manganese oxide and activated carbon composite (MnO₂-AC) were prepared by a method in which KMnO₄ was reduced by activated carbon (AC). The products were characterized by XRD and FTIR. The hybrid supercapacitor was fabricated with Li₄Mn₅O₁₂ and MnO₂-AC, which were used as materials of the two electrodes. The pseudocapacitance performance of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor was studied in various aqueous electrolytes. Electrochemical properties of the Li₄Mn₅O₁₂/MnO₂-AC hybrid supercapacitor were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the hybrid supercapacitor has electrochemical capacitance performance. The charge/discharge test showed that the specific capacitance of 51.3 F g⁻¹ was obtained within potential range of 0–1.3 V at a charge/discharge current density of 100 mA g⁻¹ in 1 mol L⁻¹ Li₂SO₄ solution. The charge/discharge mechanism of Li₄Mn₅O₁₂ and MnO₂-AC was discussed.     

Electrochemical determination of Pb<Superscript>2+</Superscript> using a carbon nanotube/Nafion composite film-modified electrode

A carbon nanotube/Nafion composite film modified electrode is described for the sensitive and convenient determination of Pb²⁺. In the presence of 1% Nafion, multi-walled carbon nanotubes (MWNT) were successfully dispersed into ethanol by ultrasonication. After evaporating the ethanol, a MWNT/Nafion composite film-modified electrode was achieved. The resulting MWNT/Nafion film modified electrode possesses high cation exchange capacity, large surface area, strong adsorption ability and catalytic activity. Compared with the unmodified electrode and Nafion film-modified electrode, the MWNT/Nafion film-modified electrode remarkably increases the stripping peak current of Pb²⁺. Furthermore, the influences of supporting electrolyte, volume of MWNT/Nafion suspension, accumulation potential and accumulation time were investigated. The striping peak current of Pb²⁺ is proportional to its concentration over the range 8.0 × 10⁻⁸ to 6.0 × 10⁻⁶ mol L⁻¹. The limit of detection (S/N = 3) is as low as 5.0 × 10⁻⁹ mol L⁻¹. Finally, this newly developed method was used to determine Pb²⁺ in water samples.     

Voltammetric studies of titanium (IV) phosphate modified with copper hexacyanoferrate and electroanalytical determination of <Emphasis Type="Italic">N</Emphasis>-acetylcysteine

Titanium (IV) Phosphate copper hexacyanoferrate composite (TiPhCuHCF) was prepared using a new methodology for the synthesis. A preliminary characterization of the precursor and resulting materials was defined using spectroscopic and chemical techniques. The cyclic voltammogram of the modified electrode containing TiPhCuHCF exhibited two redox couples. The first and second redox couples present a formal potential (E ^θ′) of 0.18 and 0.76 V and were ascribed to the Cu^+/Cu²⁺ (E ^θ′)₁ and Fe²⁺(CN)₆/Fe³⁺(CN)₆ (E ^θ′)₂ processes, respectively. In a preliminary study, the peak located at 0.76 V displays a sensitive response to N-acetylcysteine. The modified graphite paste electrode showed a linear range from 1.0 × 10⁻⁵ to 7.0 × 10⁻⁴ mol L⁻¹ for the determination of N-acetylcysteine with a limit detection of 6.96 × 10⁻⁵ mol L⁻¹ and relative standard deviation of ± 5% (n = 3) and amperometric sensitivity of 24.79 × 10⁻³ A mol L⁻¹. The modified electrode was electrochemically stable and showed good reproducibility.     

Carbon nanotube-modified glassy carbon electrode for anodic stripping voltammetric detection of Uranyle

A multi-wall carbon nanotube (MWNT) modified glassy carbon electrode (GCE) is described for the measurement of trace levels of uranium by anodic stripping voltammetry. In a pH 4.4 NaAc-Hac buffer containing 0.010 mol L⁻¹ Mg(NO₃)₂, UO₂ ²⁺ was adsorbed onto the surface of a MWNT film coated glassy carbon electrode and then reduced at −0.40 V vs. Ag/AgCl. During the positive potential sweep the reduced uranium was oxidized and a well-defined stripping peak appeared at +0.20 V vs. Ag/AgCl. Low concentrations of Mg²⁺ significantly enhanced the stripping peak currents since they induced UO₂ ²⁺ to adsorb at the electrode surface. The response was linear up to 1.2 × 10⁻⁷ mol L⁻¹ and the relative standard deviation at 2.0 × 10⁻⁸ mol L⁻¹ uranium was 5.2%. Potential interferences were examined. The attractive behavior of the new “mercury-free” uranium sensor holds promise for on-site environmental and industrial monitoring of uranium.     

The enhancement effect of phosphomolybdic acid (H<Subscript>3</Subscript>PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>) on Pd/C catalyst for the electroreduction of hydrogen peroxide

A Pd/C electrode modified by H₃PMo₁₂O₄₀ was prepared and its catalytic performance for H₂O₂ electroreduction in acidic medium was investigated by cyclic voltammograms. Pd nanoparticles supported on Vulcan XC-72 carbon were prepared by chemical reduction of PdCl₂ in aqueous solution using NaBH₄ as the reducing agent. X-ray diffraction analysis indicated that the particle size of Pd is around 9.7 nm. The modified electrode was prepared by cyclic voltammograms in H₂SO₄ solution containing H₃PMo₁₂O₄₀. The results showed that H₃PMo₁₂O₄₀ can efficiently enhance the electrocatalytic activity for H₂O₂ electroreduction on Pd/C. The effect of H₃PMo₁₂O₄₀ content on the electrocatalytic activity of the catalyst was also investigated by CV. The best results appeared at the concentration of H₃PMo₁₂O₄₀ = 0.5 mmol L⁻¹.     

Preparation and electrochemical performance of Li-rich layered cathode material,Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript>, for lithium-ion batteries

The Li-rich layered cathode material, Li[Ni_0.2Li_0.2Mn_0.6]O₂, was synthesized via a “mixed oxalate” method, and its structural and electrochemical properties were compared with the same material synthesized by the sol–gel method. X-ray diffraction (XRD) shows that the synthesized powders have a layered O₃–LiCoO₂-type structure with the R-3m symmetry. X-ray photoelectron spectroscopy (XPS) indicates that in the above material, Ni and Mn exist in the oxidation states of +2 and +4, respectively. The layered material exhibits an excellent electrochemical performance. Its discharge capacity increases gradually from the initial value of 228 mA hg⁻¹ to a stable capacity of over 260 mA hg⁻¹ after the 10th cycle. It delivers a larger capacity of 258 mA hg⁻¹ at the 30th cycle. The dQ/dV curves suggest that the increasing capacity results from the redox-reaction of Mn⁴⁺/Mn³⁺.     

DSA electrochemical treatment of olive mill wastewater on Ti/RuO<Subscript>2</Subscript> anode

The electrochemical oxidation of olive mill wastewater (OMW) over a Ti/RuO₂ anode was studied by means of cyclic voltammetry and bulk electrolysis and compared with previous results over a Ti/IrO₂ anode. Experiments were conducted at 300–1,220 mg L⁻¹ initial chemical oxygen demand (COD) concentrations, 0.05–1.35 V versus SHE and 1.39–1.48 V versus SHE potential windows, 15–50 mA cm⁻² current densities, 0–20 mM NaCl, Na₂SO₄, or FeCl₃ concentrations, 80 °C temperature, and acidic conditions. Partial and total oxidation reactions occur with the overall rate being near first-order kinetics with respect to COD. Oxidation at 28 Ah L⁻¹ and 50 mA cm⁻² leads to quite high color and phenols removal (86 and 84%, respectively), elimination of ecotoxicity, and a satisfactory COD and total organic carbon reduction (52 and 38%, respectively). Similar performance can be achieved at the same charge (28 Ah L⁻¹) using lower current densities (15 mA cm⁻²) but in the presence of various salts. For example, COD removal is less than 7% at 28 Ah L⁻¹ in a salt-free sample, while addition of 20 mM NaCl results in 54% COD reduction. Decolorization of OMW using Ti/RuO₂ anode seems to be independent of the presence of salts in contrast with Ti/IrO₂ where addition of NaCl has a beneficial effect on decolorization.     

Photoelectrochemical characterization of the synthetic crednerite CuMnO<Subscript>2</Subscript>

High quality crednerite CuMnO₂ was prepared by solid state reaction at 950 °C under argon flow. The oxide crystallizes in a monoclinically distorted delafossite structure associated to the static Jahn–Teller (J–T) effect of Mn³⁺ ion. Thermal analysis showed that it converts reversibly to spinel Cu _x Mn_3−x O₄ at ~420 °C in air and further heating reform the crednerite above 940 °C. CuMnO₂ is p-type, narrow semiconductor band gap with a direct optical gap of 1.31 eV. It exhibits a long-term chemical stability in basic medium (KOH 0.5 M), the semi logarithmic plot gave an exchange current density of 0.2 μA cm⁻² and a corrosion potential of ~−0.1 V_SCE. The electrochemical oxygen insertion/desinsertion is evidenced from the intensity–potential characteristics. The flat band potential (V _fb = −0.26 V_SCE) and the holes density (N _A  = 5.12 × 10¹⁸ cm⁻³) were determined, respectively, by extrapolating the curve C ⁻² versus the potential to the intersection with C ⁻²  = 0 and from the slope of the Mott–Schottky plot. From photoelectrochemical measurements, the valence band formed from Cu-3d wave function is positioned at 5.24 ± 0.02 eV below vacuum. The Nyquist representation shows straight line in the high frequency range with an angle of 65° ascribed to Warburg impedance originating from oxygen intercalation and compatible with a system under mass transfer control. The electrochemical junction is modeled by an equivalent electrical circuit thanks to the Randles model.     

Comparative study of the preparation and electrochemical performance of LiNi<Subscript>1</Subscript><Subscript>/2</Subscript>Mn<Subscript>1/2</Subscript>O<Subscript>2</Subscript> electrode material for rechargeable lithium batteries

Positive electrode material LiNi_1/2Mn_1/2O₂ was synthesized via the carbonate co-precipitation method and the hydroxide precipitation route to study the effects of the precursor on its structural and electrochemical properties. The results of X-ray diffraction and Rietveld refinement show that the carbonate precursor of Ni²⁺ and Mn²⁺ exhibits one phase at a pH of 8.5, while the hydroxide deposit separates into Ni(OH)₂ and Mn(OH)₂ phases under the same experimental conditions. LiNi_1/2Mn_1/2O₂ material prepared from the hydroxide precursor shows 8.9% Li/Ni exchange and a large capacity loss of 11.3% in the first 10 cycles. By contrast, more uniform distribution of transition metal ions and stable Mn²⁺ in the carbonate precursor contribute to only 7.8% Li/Ni disorder in the obtained LiNi_1/2Mn_1/2O₂, which delivers a reversible capacity of about 182 mAh g⁻¹ at a current rate of 14 mA g⁻¹ between 2.5 and 4.8 V.     

The role of TiO<Subscript>2</Subscript> layers deposited on YSZ on the electrochemical promotion of C<Subscript>2</Subscript>H<Subscript>4</Subscript> oxidation on Pt

The electrochemical promotion of Pt/YSZ and Pt/TiO₂/YSZ catalyst-electrodes has been investigated for the model reaction of C₂H₄ oxidation in an atmospheric pressure single chamber reactor, under oxygen excess between 280 and 375 °C. It has been found that the presence of a dispersed TiO₂ thin layer between the catalyst electrode and the solid electrolyte (YSZ), results in a significant increase of the magnitude of the electrochemical promotion of catalysis (EPOC) effect. The rate enhancement ratio upon current application and the faradaic efficiency values, were found to be a factor of 2.5 and 4 respectively, higher than those in absence of TiO₂. This significantly enhanced EPOC effect via the addition of TiO₂ suggests that the presence of the porous TiO₂ layer enhances the transport of promoting O²⁻ species onto the Pt catalyst surface. This enhancement may be partly due to morphological factors, such as increased Pt dispersion and three-phase-boundary length in presence of the TiO₂ porous layer, but appears to be mainly caused by the mixed ionic-electronic conductivity of the TiO₂ layer which results to enhanced O²⁻ transport to the Pt surface via a self-driven electrochemical promotion O²⁻ transport mechanism.     

Photoelectrochemical reaction of biomass-related compounds in a biophotochemical cell comprising a nanoporous TiO<Subscript>2</Subscript> film photoanode and an O<Subscript>2</Subscript>-reducing cathode

Photoelectrochemical decomposition of bio-related compounds such as ammonia, formic acid, urea, alcohol, and glycine by a biophotochemical cell (BPCC) comprising a nanoporous TiO₂ film photoanode and an O₂-reducing cathode generating simultaneously electrical power was investigated. The bio-related compounds studied were all photodecomposed by the present BPCC when they were either liquid or soluble in water. It was shown that ethanol exhibits similar characteristics both under 1 atm O₂ and air as studied by cyclic voltammograms. Although the present BPCC utilizes only UV light, a solar simulator at AM 1.5G and 100 mW cm⁻² light intensity gave also moderate photocurrent–photovoltage (J–V) characteristics with about 2/5 of the short circuit photocurrent (J _sc) values (J _sc) of that under a Xe lamp irradiation at the intensity of 503 mW cm⁻². It was demonstrated that varieties of bio-related compounds can be used as a direct fuel simultaneously for photodecomposition and electrical power generation. The charge transport processes in the BPCC operation were analyzed using glycine by an alternating current impedance spectroscopy, showing that the charge transfer reactions on the photoanode and the cathode surfaces compose the major resistance for the cell performance.     

Improved performances of mechanical-activated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/MWNTs cathode for aqueous rechargeable lithium batteries

LiMn₂O₄/multi-walled carbon nanotubes (MWNTs) composite was synthesized by mechanical activation reaction followed by a heat-treatment (500 °C). The LiMn₂O₄ and LiMn₂O₄/MWNTs as cathodes were investigated in 1 M Li₂SO₄ by cyclic voltammetry (CV), galvanostatic charge/discharge (GC), and electrochemical impedance spectroscopy (EIS). The LiMn₂O₄/MWNTs cathode delivered higher discharge capacity (117 mAh g⁻¹) than LiMn₂O₄ (84.6 mAh g⁻¹). Furthermore, the results from EIS showed that LiMn₂O₄/MWNTs had a faster kinetic process for lithium ion intercalation/de-intercalation than LiMn₂O₄. Besides, LiMn₂O₄/MWNTs had better cycling stability and rate capability than LiMn₂O₄, which was confirmed by GC testing. SEM images showed that a three-dimensional network structure was formed during the mechanical activation, giving a decrease of particle size.     

Voltammetric behavior and the determination of quercetin at a flowerlike Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles modified glassy carbon electrode

Flowerlike Co₃O₄ nanoparticles were used as a modifier on the glassy carbon electrode to fabricate a quercetin (Qu) sensor. The morphology and crystallinity of the prepared Co₃O₄ material were investigated by scanning electron microscopy and X-ray diffraction. Electrochemical behavior of Qu at the sensor was studied by cyclic voltammetry and semi-derivative voltammetry. Results suggested that the modified electrode exhibited a strong electrocatalytic activity toward the redox of Qu. The electron transfer coefficient (α), the number of electron transfer (n), and the diffusion coefficient (D) of Qu at the sensor were calculated. Under the optimum conditions, the catalytic peak currents of Qu were linearly dependent on the concentrations of Qu in the range from 5.0 × 10⁻⁷ to 3.3 × 10⁻⁴ M, with a detection limit of 1.0 × 10⁻⁷ M. This proposed method was successfully applied to determine the quercetin concentration in Ginkgo leaf tablet and human urine samples.     

Facile Solvothermal Synthesis Ni(OH)<Subscript>2</Subscript> Nanostructure for Electrochemical Capacitors

Nickel hydroxide nanosheets were successfully synthesized by facile solvothermal method without any template. The structure and morphology of the as-prepared sample were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. The observations revealed the formation of hexagonal phase β-Ni(OH)₂ nanosheets with an average diameter of about 100–120 nm. Electrochemical studies were carried out using cyclic voltammetry and galvanostatic charge–discharge tests, respectively. A maximum specific capacitance of 2,342 F g⁻¹, which is the highest reported for a β-Ni(OH)₂ electrode, could be achieved in 6 mol L⁻¹ KOH electrolyte within the potential range of 0–0.50 V (vs. SCE) for the obtained β-Ni(OH)₂ electrode at 0.4 A g⁻¹, suggesting its potential application in the electrode material for electrochemical capacitors.     

Effects of surface area on electrochemical performance of Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript> cathode material

The effect of surface area on the electrochemical properties and thermal stability of Li[Ni_0.2Li_0.2Mn_0.6]O₂ powders was characterized using a charge/discharge cycler and DSC (Differential Scanning Calorimeter). The surface area of the samples was successfully controlled from ~4.0 to ~11.7 m² g⁻¹ by changing the molar ratio of the nitrate/acetate sources and adding an organic solvent such as acetic acid or glucose. The discharge capacity and rate capability was almost linearly increased with increase in surface area of the sample powder. A sample with a large surface area of 9.6–11.7 m² g⁻¹ delivered a high discharge capacity of ~250 mAh g⁻¹ at a 0.2 C rate and maintained 62–63% of its capacity at a 6 C rate versus a 0.2 C rate. According to the DSC analysis, heat generation by thermal reaction between the charged electrode and electrolyte was not critically dependent on the surface area. Instead, it was closely related to the type of organic solvent employed in the fabrication process of the powder.     

Determination of hydrogenation ability and exchange current of H<Subscript>2</Subscript>O/H<Subscript>2</Subscript> system on hydrogen-absorbing metal alloys

A detailed analysis of potential versus time measurements at galvanostatic charge/discharge conditions (external current change from −1 to +1 mA cm⁻²) for two La–Ni alloys in Ar-saturated 0.1 M KOH solution is presented. It is shown that passivation of the electrodes does not affect the potential jump as a result of current switching over. The value of potential jump allows to calculate the exchange current density for H₂O/H₂ system on the tested material. Anodic potential of the hydrogenated electrode (at i _a = const) linearly increases with logarithm of time which allows to evaluate precisely time necessary for oxidation of hydrogen absorbed during cathodic charging. The method described enables to determine effectiveness of hydrogen absorption by materials applied for negative electrodes of NiMH batteries.     

Study on the properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-BaO lead-free glass using in the electronic pastes

The Sb₂O₃ doping lead-free glass in Bi₂O₃-B₂O₃-BaO ternary system were prepared in the composition of several different subsystem, and the glass powder was produced through the process of water quenching. Glass transition temperatures (T _g ), glass soften temperatures(T _s ), the volume resistivity (ρ) in the temperature range of 80–200°C, and linear thermal coefficients of expansion in the temperatures range of 25–300°C (α_25–300) were measured for subsystems along with the different ratio of Bi₂O₃, B₂O₃ and BaO. For these subsystems, T _g ranged from 458 to 481°C, and T _s ranged from 490 to 512°C, both decreasing with the increasing of Bi₂O₃/B₂O₃ ratio, and increasing with the increasing of BaO/B₂O₃ ratio. The measured α_25–300 ranged from 65.3 to 76.3 × 10⁻⁷ K⁻¹, with values increasing with increasing Bi₂O₃/B₂O₃ and BaO/B₂O₃ ratio. The volume resistivity remains at a high standards, which may caused by it’s non-alkali composition, and it fluctuated from 10¹³ to 10¹¹ Ω cm with the temperature varied from 80–200°C. The structure of Bi₂O₃-B₂O₃-BaO ternary leadfree glass system was mearsured by FT-IR. The IR studies indicate that these glasses are made up of [BiO₆], [BO₃], and [BO₄] basic structural units, and it appears that Ba²⁺ acts as a glass-modifier in this ternary system, but the Bi³⁺ has entered the glass network when it is in relative high content so as to change the α_25–300, T _s and T _g .