Chemical Engineering / Kimya Mühendisliği
Permanent URI for this collectionhttps://hdl.handle.net/11147/14
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Article Citation - WoS: 3Validation on of Local Thermal Equilibrium and Uniform Pressure Assumptions for an Isobaric Adsorption Process in an Adsorbent Bed(Türk Isı Bilimi ve Tekniği Derneği, 2016) Gediz İliş, Gamze; Mobedi, Moghtada; Ülkü, SemraBu çalışmanın amacı, adsorbent yatakta ısı ve kütle transferini analiz etmek için kullanılan yerel ısıl denge ve sabit basınç yaklaşımı varsayımların geçerliliğini araştırmaktır. İçerisinde silika jel partikülleri içeren bir yatak ile su kabı olan bir deney düzeneği tasarlanmış ve adsorpsiyon sürecinde yatağın içinde farklı yerlerde yerel sıcaklık ve basınç ölçülmüştür. Ayrıca, sabit basınç yaklaşımı ve yerel ısıl denge varsayımlara dayalı ısı ve kütle transferi denklemleri çözülmüştür. Sayısal sonuçlar, ilgili deneysel sonuçlarla karşılaştırılmış ve aralarında oldukça iyi bir uyum tespit edilmiştir. Gerçekleştirilen karşılaştırmaya dayanarak, incelenen yatak için iki önemli sonuç şu şekildedir: a) katı madde ve su buharı arasında yerel ısıl denge bulunmaktadır, b) bir yatak içinde parçacıklar arası kütle transferi direnci ihmal edilebilir düzeyde olup konsantrasyonunun ve sıcaklığın belirlenmesi için sabit basınç yaklaşımı geçerlidir. Ayrıca, bu çalışmada sunulan deneysel sonuçlar diğer araştırmacıların sayısal çalışmalarının geçerliliğini doğtulamak için değerli veriler sağlayacaktır.Article Citation - WoS: 13Citation - Scopus: 13Application of Work Function Measurements in the Study of Surface Catalyzed Reactions on Rh(1 0 0)(Taylor & Francis, 2018) Çağlar, Başar; Kızılkaya, Ali Can; Niemantsverdriet, J. W. (Hans); Weststrated, C. J. (Kees-Jan)The present article aims to show how work function measurements (WF) can be applied in the study of elementary surface reaction steps on metallic single crystal surfaces. The work function itself can in many cases not be interpreted directly, as it lacks direct information on structural and chemical nature of the surface and adsorbates, but it can be a powerful tool when used together with other surface science techniques which provide information on the chemical nature of the adsorbed species. We here, illustrate the usefulness of work function measurements using Rh(100) as our model catalyst. The examples presented include work function measurements during adsorption, surface reaction, and desorption of a variety of molecules relevant for heterogeneous catalysis. Surface coverage of adsorbates, isosteric heat of adsorption, and kinetic parameters for desorption, desorption/decomposition temperatures of surface species, different reaction regimes were determined by WF with the aid of other surface science techniques.Article Citation - WoS: 5Citation - Scopus: 6Development of an Optical Tyrosinase Biosensor (tca) for Detection of “parathion-Methyl”(Emerald Group Publishing Ltd., 2019) Polatoğlu, İlker; Çakıcıoğlu Özkan, FehimePurpose: This paper aims to present a novel and cost-effective optical biosensor design by simple preparation method for detection of “parathion-methyl,” which is a model pesticide pose to public health and the environment. Design/methodology/approach: The optical enzyme biosensor (TCA) for detection of pesticide “parathion-methyl” was developed on the basis of immobilization of tyrosinase enzyme on chitosan film by adsorption technique. The analytic performance of TCA was investigated by measuring its activity with Ultraviolet (UV) visible spectrophotometer. Findings: Uniform porous network structure and protonated groups of chitosan film provided a microenvironment for tyrosinase immobilization evident from Fourier transform infrared (FTIR) spectroscopy and Atomic Force Microscopy analysis. TCA has a wide linear detection range (0-1.03 µM) with high correlation coefficient and it can detect the parathion-methyl concentration as low as 159 nM by noncompetitive inhibition kinetics. Using the TCA sensor both for ten times and at least 45 days without a significant loss in its activity are the indicators of its good operational and storage stability. Moreover, TCA can be applicable to tap water, providing a promising tool for pesticides detection. Originality/value: This is the first time to use the in situ analytical technique that can improve the performance of optical enzyme sensor provided to control the pesticide residue better with respect to traditional techniques. The effect of organic solvents on the performance of optical enzyme biosensor was investigated. Inhibition kinetic of the solvents rarely encountered in literature was also studied besides the pH and temperature tolerance of the optical biosensor.Article Citation - WoS: 18Citation - Scopus: 21Polybrominated Diphenyl Ethers (pbdes) in Background Air Around the Aegean: Implications for Phase Partitioning and Size Distribution(Springer Verlag, 2017) Besis, Athanasios; Lammel, Gerhard; Kukucka, Petr; Samara, Constantini; Sofuoğlu, Aysun; Dumanoğlu, Yetkin; Eleftheriadis, Kostas; Kouvarakis, Giorgos; Sofuoğlu, Sait Cemil; Vassilatou, Vassiliki; Voutsa, DimitraThe occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑7PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m−3, respectively) were found at the remote site Finokalia. Partitioning coefficients, KP, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (PL°) and the octanol-air partition coefficient (KOA), were investigated. The equilibrium adsorption (PL°-based) and absorption (KOA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log KOA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log PL° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.Article Citation - WoS: 3Citation - Scopus: 5Adsorption Characteristics of Lead-, Barium- and Hydrogen-Rich Clinoptilolite Mineral(SAGE Publications Inc., 2003) Çakıcıoğlu Özkan, Seher Fehime; Ülkü, SemraThe carbon dioxide and water vapour adsorption properties of local clinoptilolite-rich material, both as the original and as lead-, barium- and hydrogen-rich forms, were examined. The lead- and barium-rich forms were prepared by treatment of the original clinoptilolite with Pb(NO3)2 and BaCl2 respectively, while the hydrogen-rich form was prepared by NH4Cl and heat treatment. Water and CO2 adsorption experiments were conducted in a volumetric system under static conditions, with low-pressure adsorption data being used for the characterization of the natural, Pb-rich, Ba-rich and H-rich clinoptilolite samples. Although the existence of barium-exchange was not noted, an appreciable decrease in CO2 adsorption was observed with the Pb-rich and H-rich forms due to a decrease in the electrostatic interaction between the surface and the adsorbate. Application of the Dubinin-Astakhov equation to the water adsorption data established the existence of micropores of different sizes that exhibited different adsorption mechanisms.Article Citation - WoS: 23Citation - Scopus: 29Dynamic Nature of Supercritical Co2 Adsorption on Coals(Springer Verlag, 2017) Özdemir, EkremAdsorption on non-rigid solids was shown to be a dynamic process. Excess adsorption and desorption isotherms of CO2 on eight Argonne Premium coal samples were measured at 55 °C and pressures up to 14 MPa by manometric method. The excess adsorption isotherms of CO2 on powdered coals showed almost Langmuir-like to rectilinear shape behavior at low pressures up to 9 MPa, and it increased noticeably at pressures higher than 9 MPa. There was a significant hysteresis between the excess adsorption and desorption isotherms for each rank of coals, which was related to the volumetric uncertainties occurring during the adsorption isotherm measurements. The parameters related to the adsorption capacity and micro porous characteristics of the coal were obtained at different pressure ranges by fitting the experimental data to the modified Dubinin-Astakhov (D-A) equation at the increasingly larger pressure ranges, using only the first 4 data points of the excess adsorption isotherm initially, and progressively using additional data points for the subsequent values. It was shown that the curve fit parameters vary with pressure, and therefore, concluded that the adsorption on non-rigid solids such as CO2 on coal is indeed a dynamic process. It was suggested that new adsorption isotherm equations need to be developed considering the dynamic nature of the adsorption on solid adsorbents.Article Citation - WoS: 55Citation - Scopus: 60Effect of Regeneration Temperature on Adsorption Equilibria and Mass Diffusivity of Zeolite 13x-Water Pair(Elsevier Ltd., 2016) Sayılgan, Şefika Çağla; Mobedi, Moghtada; Ülkü, SemraThe adsorption equilibrium and mass diffusivity of zeolite 13X-water pair for different adsorption and regeneration temperatures were determined by a homemade volumetric system. The isotherms of the zeolite 13X-water pair were obtained by collecting pressure versus time data and applying ideal gas law. The effective diffusivity of the pair was calculated by using long term analytical solution of mass diffusivity based on Fick's law. The experimental study showed that the adsorption capacity of zeolite 13X-water pair was 23% (kg/kg), 21% (kg/kg) and 19% (kg/kg) when the adsorption temperature was 35, 45 and 60 °C respectively for the desorption temperature of 90 °C. Furthermore, the adsorption capacity increased from 22% (kg/kg) to 24% (kg/kg) when the desorption temperature was increased from 90 °C to 150 °C. It was observed that the present adsorption equilibrium results were compatible with the reported results in the literature. The mass diffusivity of the pair was found in the range of 4 × 10-9-6 × 10-8 m2/s for the long time period when the initial adsorptive pressure was 2000 Pa. The effective mass diffusivity depends on concentration and it was decreased with increasing adsorbate concentration.Article Citation - WoS: 21Citation - Scopus: 22Role of Ph on Co2 Sequestration in Coal Seams(Elsevier Ltd., 2016) Özdemir, EkremThe effect of acidic or basic pre-treatment on the adsorption capacity of CO2 on coals was investigated. Argonne Premium Pocahontas No. 3, Upper Freeport, Pittsburgh No. 8, Lewiston-Stockton, Blind Canyon, Illinois No. 6, Wyodak, and Beulah-Zap coals were washed in weak solutions of H2SO4 and NaOH to the pH values of 10, 7, and 2, after an initial washing in acidic water. Attempts to treat the Wyodak and Beulah-Zap coals were unsuccessful because the base treatment after the initial acid treatment resulted in a suspension which could be separated neither via filtration through a 45 μm filter nor centrifugation. Equilibration took several days in some cases, although the as-received coal had been ground to 150 μm. Acid washing preferentially removed Ca (calcite) and Mg. Aluminosilicate clays were not notably removed. Iron was removed in significant amounts only after base treatment, possibly after it was converted to hematite. The adsorption capacity of CO2 on the acid treated coals was higher than both the base treated and untreated coals. The difference in adsorption capacities for acid and base treated coals was related to the pore sizes and mineral matter removal from the coals, where the calculated average pore size was higher for acid treated coals than for the base treated coals. It is concluded that the pH decrease due to CO2 dissolution in cleat water is favored in coal seam sequestration, which resulted in an increase in storage capacity of coals.Article Citation - WoS: 3Citation - Scopus: 2Adsorption of No in Clinoptilolite-Rich Zeolitic Mineral by Concentration Pulse Chromatography Method(Elsevier Ltd., 2016) Narin, Güler; Ülkü, SemraThe equilibrium and kinetic parameters for NO adsorption in a clinoptilolite-rich natural zeolitic material from Turkey were determined using the concentration pulse chromatography method. Under the experimental conditions (carrier gas velocities and adsorption temperatures) the micropore diffusion resistance was found to be the mass transfer controlling step. Matching the first moment of the response peaks to the mathematical model the Henry's Law constants and heat of adsorption at zero loading were determined. The axial dispersion, external film, macropore and micropore diffusion coefficients, and activation energy for diffusion of NO in the micropores were calculated from the analysis of the second moments of the response peaks. For successive NO pulses without regeneration between the pulses, the retention times of the response peaks decreased and peak areas increased with the injection number indicating irreversible adsorption. The reversibly adsorbed NO could be desorbed by purging with an inert gas at the adsorption pressure and temperature. Temperature programmed desorption profile obtained by heating the NO saturated adsorbent to 400 °C under inert flow revealed presence of multiple irreversibly adsorbed species in NZ with different thermal stabilities. Desorption of these species was not achieved during the heating up to 400 °C which makes the natural zeolitic materıal suitable for NO storage rather than for cyclic adsorptive separation processes.Article Citation - WoS: 5Citation - Scopus: 5Methylene Blue Adsorption From Aqueous Solutions To Flexible Poly(vinyl Chloride) Silica Composites(John Wiley and Sons Inc., 2015) Yetgin, Senem; Ulutan, Sevgi; Balköse, DevrimMethylene blue (MB) adsorption studies were performed with poly(vinyl chloride)-(dioctyl phthalate)-silica composites, which were obtained by using plastisol-plastigel technology. The films were flexible, having elastic modulus of 1.0-1.5 GPa. Diminishing MB concentration in the aqueous phase was followed as the adsorption process advanced by using visible spectroscopy. Contributions of the individual components of the composites to adsorption were also investigated. Although the MB adsorption capacity was extensively high for silica, it was moderate for the composite, most likely owing to the occlusion of pores of silica by plasticizer to some extent. The improvement of MB adsorption capacity of the composites as the silica ratio increased was explicitly deduced from the optical microscopy photographs. The diffusion coefficients of MB through the composites were 5 × 10-13, 6 × 10-13, and 3 × 10-13 m2 s-1 with regression coefficients of 0.73, 0.89, and 0.88 for 0, 2, and 16% silica-containing composites, respectively. Because of the slow diffusion of MB in poly(vinyl chloride)-silica composites, using them as dynamic column adsorbent was not practical. However, these versatile plastics can be used as plastic labels, colored clothing, leather substitutes, antimicrobial medical devices, and laser printable surfaces.