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Larisa Karpenko-Jereb

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Papers by Larisa Karpenko-Jereb

Research paper thumbnail of Conductometric and computational study of cation-exchange membranes in H+ and Na+ forms with the various hydration level

Knowledge of the correlation between the molecular polyelectrolyte structure of membranes and the... more Knowledge of the correlation between the molecular polyelectrolyte structure of membranes and their transport properties helps to develop new ion-exchange polymers with improved characteristics. This research paper studies the transport properties of two counter-ions, H + and Na + , inside four commercial cationic membranes with experimental methods: three aromatic hydrocarbon polymer membranes CM-1, CMX, MK-40, and one tetrafluoroethylene polymer Nafion analog membrane MF-4SK. Ab initio calculations of the membrane structures with various hydration levels were applied in order to interpret the difference in the transport parameters of counter-ions between aromatic hydrocarbon MK-40 and non-aromatic perfluorinated MF-4SK polymer membranes. The membrane physico-chemical characteristics and the conductivity were experimentally investigated as a function of NaCl and HCl aqueous solution concentration. The conductivity and diffusion coefficients of the counter-ions, as well as volume fractions of 'gel' and 'inter-gel' phases were determined based on the microheterogeneous two-phase model. For the first time, ab initio calculations on membrane models were correlated with experimental findings in order to explain the difference in the mobility of the two counter-ions. The static ab initio study indicates the dissociation of the functional groups and a stronger water connectivity in perfluorinated membrane, providing an explanation for the measured highest diffusion coefficient and molar conductivity of the counter-ions H + and Na + in MF-4SK membrane in comparison to MK-40 membrane.

Research paper thumbnail of Transport and equilibrium properties of sulfonic ion-exchange membranes

Research paper thumbnail of Polymer Electrolyte Membrane Fuel Cells: fundamentals, performance and degradation

Research paper thumbnail of On the Schroeder paradox for ion-exchange polymers

Colloid journal of the Russian Academy of Sciences, Nov 1, 2016

The known Schroeder paradox, i.e., a difference in the degree of swelling of ion-exchange polymer... more The known Schroeder paradox, i.e., a difference in the degree of swelling of ion-exchange polymers at equilibrium with liquid water and its vapor, has been discussed. It has been noted that there is no paradoxicality in this phenomenon. An example of different "swelling" based on trivial physical considerations has been presented. A simple mechanism has been proposed for increased swelling of an ion-exchange polymer immersed in liquid water, this mechanism being associated with the action of the Maxwell stresses at a polymer/electrolyte interface. The predicted values of the "excess" swelling have been shown to correspond to the data of real experiments.

Research paper thumbnail of Development of experimental method to measure membrane conductivity

Measurement of the stationary nucleation rate as a function of supersaturation in reactive precip... more Measurement of the stationary nucleation rate as a function of supersaturation in reactive precipitation requires that nucleation and growth of the crystals to an observable size take place under well-controlled hydrodynamic conditions and at a constant supersaturation. An experimental method was chosen that is based on the measurement of the increase of the particle concentration with the increase of the residence time in a precipitation tube. This method was applied to measure the nucleation rate for the pH shift precipitation of the molecular compound H 4 EDTA. The parameters A and B in the classical nucleation theory equation were derived from the measured nucleation rates. A value of A) (5.7 (1.0) × 10 15 m-3 s-1 was found for the intercept with the ordinate and a value of B) (3.3 (2.0) × 10 2 was found for the slope. The estimated value for parameter A is lower than the theoretical value of A HON) 10 33 m-3 s-1 for homogeneous nucleation. Using the experimentally determined value for B the interfacial energy is found to be γ) 21 (9 mJ m-2 compared to a theoretical value of γ HON) 38 mJ m-2 based on bulk properties. The experimentally obtained values for A and γ indicate heterogeneous nucleation.

Research paper thumbnail of Study of sulfonic acid group dissociation and water connectivity in polystyrene and perfluorinated membranes

Research paper thumbnail of History of Conductometric Method of Analysis

Journal of Analytical Chemistry, 2014

Research paper thumbnail of Carl Remigius Fresenius. To 150th Anniversary of the first Journal of Analytical Chemistry

Journal of Analytical Chemistry, 2013

Research paper thumbnail of Modeling of the impact of cycling operating conditions on durability of polymer electrolyte fuel cells and its sensitivity analysis

International Journal of Hydrogen Energy, 2023

Research paper thumbnail of Theoretical and experimental investigation of Nafion(R)-Li+ and IonClad(TM)-Li+ membranes in contact with water and methanol

Research paper thumbnail of Interaction of cation exchange membrane with the solvent methanol and water

Research paper thumbnail of Interaction of polyelectrolyte membranes with water: a theoretical study

Research paper thumbnail of Polymer Electrolyte Fuel Cells

Elsevier eBooks, 2018

Abstract This chapter describes the main components of the polymer electrolyte fuel cell and its ... more Abstract This chapter describes the main components of the polymer electrolyte fuel cell and its role in cell performance. It presents five synthesis routes for the preparation of electrocatalysts, and discusses the influence of nanoparticle formation on the catalytic properties. Regarding the polymer electrolyte membranes, the chapter explains proton transport within membranes based on their structural features. Physicochemical and transport properties characterizing the membranes are described as well. The chapter further highlights the importance of bipolar plates in general, the selection of suitable bipolar plate materials, and different flow-field designs.

Research paper thumbnail of Effect of polymer and counter-ion nature on the structural features of the polymer electrolyte membranes: Key lecture

Research paper thumbnail of О ПАРАДОКСЕ ШРОЕДЕРА ДЛЯ НЕИОНОГЕННЫХ ПОЛИМЕРОВ, "Коллоидный журнал

Research paper thumbnail of Restricted Hartree-Fock Investigation of Nafion Membrane in Water and Methanol

International Scientific Conference on Pervaporation, Vapor Permeation and Membrane Distillation, 2013

Research paper thumbnail of О ПАРАДОКСЕ ШРОЕДЕРА ДЛЯ НЕИОНОГЕННЫХ ПОЛИМЕРОВ, "Коллоидный журнал

Research paper thumbnail of Polymer Electrolyte Membrane Fuel Cells: fundamentals, performance and degradation

Research paper thumbnail of History of Conductometric Method of Analysis

Journal of Analytical Chemistry, 2014

Research paper thumbnail of Effect of polymer and counter-ion nature on the structural features of the polymer electrolyte membranes: Key lecture

Research paper thumbnail of Conductometric and computational study of cation-exchange membranes in H+ and Na+ forms with the various hydration level

Knowledge of the correlation between the molecular polyelectrolyte structure of membranes and the... more Knowledge of the correlation between the molecular polyelectrolyte structure of membranes and their transport properties helps to develop new ion-exchange polymers with improved characteristics. This research paper studies the transport properties of two counter-ions, H + and Na + , inside four commercial cationic membranes with experimental methods: three aromatic hydrocarbon polymer membranes CM-1, CMX, MK-40, and one tetrafluoroethylene polymer Nafion analog membrane MF-4SK. Ab initio calculations of the membrane structures with various hydration levels were applied in order to interpret the difference in the transport parameters of counter-ions between aromatic hydrocarbon MK-40 and non-aromatic perfluorinated MF-4SK polymer membranes. The membrane physico-chemical characteristics and the conductivity were experimentally investigated as a function of NaCl and HCl aqueous solution concentration. The conductivity and diffusion coefficients of the counter-ions, as well as volume fractions of 'gel' and 'inter-gel' phases were determined based on the microheterogeneous two-phase model. For the first time, ab initio calculations on membrane models were correlated with experimental findings in order to explain the difference in the mobility of the two counter-ions. The static ab initio study indicates the dissociation of the functional groups and a stronger water connectivity in perfluorinated membrane, providing an explanation for the measured highest diffusion coefficient and molar conductivity of the counter-ions H + and Na + in MF-4SK membrane in comparison to MK-40 membrane.

Research paper thumbnail of Transport and equilibrium properties of sulfonic ion-exchange membranes

Research paper thumbnail of Polymer Electrolyte Membrane Fuel Cells: fundamentals, performance and degradation

Research paper thumbnail of On the Schroeder paradox for ion-exchange polymers

Colloid journal of the Russian Academy of Sciences, Nov 1, 2016

The known Schroeder paradox, i.e., a difference in the degree of swelling of ion-exchange polymer... more The known Schroeder paradox, i.e., a difference in the degree of swelling of ion-exchange polymers at equilibrium with liquid water and its vapor, has been discussed. It has been noted that there is no paradoxicality in this phenomenon. An example of different "swelling" based on trivial physical considerations has been presented. A simple mechanism has been proposed for increased swelling of an ion-exchange polymer immersed in liquid water, this mechanism being associated with the action of the Maxwell stresses at a polymer/electrolyte interface. The predicted values of the "excess" swelling have been shown to correspond to the data of real experiments.

Research paper thumbnail of Development of experimental method to measure membrane conductivity

Measurement of the stationary nucleation rate as a function of supersaturation in reactive precip... more Measurement of the stationary nucleation rate as a function of supersaturation in reactive precipitation requires that nucleation and growth of the crystals to an observable size take place under well-controlled hydrodynamic conditions and at a constant supersaturation. An experimental method was chosen that is based on the measurement of the increase of the particle concentration with the increase of the residence time in a precipitation tube. This method was applied to measure the nucleation rate for the pH shift precipitation of the molecular compound H 4 EDTA. The parameters A and B in the classical nucleation theory equation were derived from the measured nucleation rates. A value of A) (5.7 (1.0) × 10 15 m-3 s-1 was found for the intercept with the ordinate and a value of B) (3.3 (2.0) × 10 2 was found for the slope. The estimated value for parameter A is lower than the theoretical value of A HON) 10 33 m-3 s-1 for homogeneous nucleation. Using the experimentally determined value for B the interfacial energy is found to be γ) 21 (9 mJ m-2 compared to a theoretical value of γ HON) 38 mJ m-2 based on bulk properties. The experimentally obtained values for A and γ indicate heterogeneous nucleation.

Research paper thumbnail of Study of sulfonic acid group dissociation and water connectivity in polystyrene and perfluorinated membranes

Research paper thumbnail of History of Conductometric Method of Analysis

Journal of Analytical Chemistry, 2014

Research paper thumbnail of Carl Remigius Fresenius. To 150th Anniversary of the first Journal of Analytical Chemistry

Journal of Analytical Chemistry, 2013

Research paper thumbnail of Modeling of the impact of cycling operating conditions on durability of polymer electrolyte fuel cells and its sensitivity analysis

International Journal of Hydrogen Energy, 2023

Research paper thumbnail of Theoretical and experimental investigation of Nafion(R)-Li+ and IonClad(TM)-Li+ membranes in contact with water and methanol

Research paper thumbnail of Interaction of cation exchange membrane with the solvent methanol and water

Research paper thumbnail of Interaction of polyelectrolyte membranes with water: a theoretical study

Research paper thumbnail of Polymer Electrolyte Fuel Cells

Elsevier eBooks, 2018

Abstract This chapter describes the main components of the polymer electrolyte fuel cell and its ... more Abstract This chapter describes the main components of the polymer electrolyte fuel cell and its role in cell performance. It presents five synthesis routes for the preparation of electrocatalysts, and discusses the influence of nanoparticle formation on the catalytic properties. Regarding the polymer electrolyte membranes, the chapter explains proton transport within membranes based on their structural features. Physicochemical and transport properties characterizing the membranes are described as well. The chapter further highlights the importance of bipolar plates in general, the selection of suitable bipolar plate materials, and different flow-field designs.

Research paper thumbnail of Effect of polymer and counter-ion nature on the structural features of the polymer electrolyte membranes: Key lecture

Research paper thumbnail of О ПАРАДОКСЕ ШРОЕДЕРА ДЛЯ НЕИОНОГЕННЫХ ПОЛИМЕРОВ, "Коллоидный журнал

Research paper thumbnail of Restricted Hartree-Fock Investigation of Nafion Membrane in Water and Methanol

International Scientific Conference on Pervaporation, Vapor Permeation and Membrane Distillation, 2013

Research paper thumbnail of О ПАРАДОКСЕ ШРОЕДЕРА ДЛЯ НЕИОНОГЕННЫХ ПОЛИМЕРОВ, "Коллоидный журнал

Research paper thumbnail of Polymer Electrolyte Membrane Fuel Cells: fundamentals, performance and degradation

Research paper thumbnail of History of Conductometric Method of Analysis

Journal of Analytical Chemistry, 2014

Research paper thumbnail of Effect of polymer and counter-ion nature on the structural features of the polymer electrolyte membranes: Key lecture

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