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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Lithium Recovery and Conversion from Wastewater Produced by Recycling of Li-Ion Batteries via Two-Stage Electrodialysis

Electrodialysis (ED) is a membrane separation technique that has been well-established in various applications such as desalination, drinking water production, wastewater treatment, and lithium salt production. A limited number of studies have explored its application in lithium salt production, especially from secondary resources like wastewater. This study investigated a route to recover lithium from wastewater generated from the recycling of end-of-life Li-ion batteries. Two electrodialysis methods, namely standard electrodialysis (ED) and bipolar-membrane electrodialysis (BPED), were combined to concentrate lithium ions and convert them to lithium hydroxide (LiOH), a valuable product that can be fed back into the supply chain for manufacturing Li-ion batteries. Lithium (Li⁺) concentration in recycling wastewater was successfully increased by 58% using ED and converted to LiOH (>96% purity) with a further increase in Li⁺ concentration by 67% using BPED. The Coulombic efficiency of the experiments was 91.0 and 92.2%, with specific energy consumption of 1 and 2.5 kWh/kg, and a production rate of 1.01 and 0.14 kg/h/m 2 for the ED and BPED processes, respectively. In addition, preliminary techno-economic and environmental impact analyses show a significant improvement (GHG emission reduction by 77% and total energy reduction by 53%) by producing LiOH via electrodialysis compared to conventional lithium production via brine extraction. The process was assessed to be beneficial for lithium extraction from secondary resources and to enhance overall battery recycling efforts.

25 ENERGY STORAGE↗
DOE OSTI2023

Final Report for Water Electrodialysis Reversal Pilot

This final report presents all the work and tests performed during ION Clean Energy’s Water Electrodialysis Reversal Pilot referred to as the “WERP” Project (DE-FE-0032066). ION Clean Energy Engineering (ION) and Nebraska Public Power District (NPPD) executed the Electrodialysis Reversal (EDR) Pilot Study and developed a commercial cost estimate needed to evaluate the retrofit of an EDR system to NPPD’s Gerald Gentleman Station (GGS). The proven project team was comprised of NPPD, Sargent & Lundy (S&L) and ElectroSep, who is a leading developer, fabricator and operator of electrodialysis units. ION, working in conjunction with NPPD and ElectoSep, developed a test program for evaluating the performance of the EDR technology proposed to be employed and evaluated for this pilot. The Department of Energy’s National Energy and Technology Laboratory (DOE/NETL) awarded ION Clean Energy, Inc. a single budget period (BP) of $816,759 with $207,942 of in-kind contribution from NPPD to investigate ElectroSep’s Electrodialysis technology to clean grey water from NPPD’s GGS.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Selective concentration of multivalent cations via electrodialysis through tandem membranes

Selective electrodialysis is attractive for recovering and recycling valuable ions. However, most studies in this field focus on membranes that are selective for monovalent ions. Multivalent cations preferentially partition into cation-exchange membranes, but low mobilities and concentration polarization limit electrodialysis selectivities for these cations. This work employs electrodialysis through an “in-series” combination of a Nafion membrane and a multilayer polyelectrolyte film (MPF)-coated Nafion membrane to concentrate and isolate La 3+ or Mg 2+ from monovalent ions. The bare Nafion membrane gives a La 3+ /Na + selectivity up to 4 (depending on conditions), which enables concentration of La 3+ with a high current efficiency. The MPF-coated membrane allows selective passage of Na + while rejecting La 3+ to increase the purity of the concentrated multivalent cation. For example, the concentration of La 3+ in the accumulation solution can reach 9 times its original concentration in the feed solution with a purity of 93 mol% (99 wt%) when starting with equimolar mixtures of NaNO 3 and La(NO 3 ) 3 . This study examines how the separation varies with the type of polyelectrolyte, the applied voltage, and the composition of feed, accumulation, and cathode solutions. Here, a high nitric acid concentration (0.5 M) in the cathode compartment allows monovalent anions to pass through the MPF-coated Nafion membrane to maintain the electroneutrality of the accumulation solution. With a low acid concentration (0.04 M) in the cathode chamber, water splitting occurs at the MPF-coated membrane and La(OH) 3 precipitates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Comparison of the Effects of Bipolar Membrane Preparation Conditions on the Mechanical Durability and Electrochemical Performance for Electrodialysis Applications

Bipolar membranes (BPMs) are enabling materials for electrochemical conversion technologies such as water electrolysis, fuel cells, CO 2 electrolysis, and electrodialysis (ED) for direct air/ocean capture of CO 2 . However, current BPM durability can suffer from chemical, mechanical, and performance degradation when operated at high current density (ion flux) and physical scale. Therefore, this limits its adoption in a wider applications space. BPMs have several known degradation mechanisms, including chemical breakdown of ion-exchange polymers, loss of junction adhesion, or physical breakdown due to shearing force and pressure swings in an electrodialysis cell. To assess the electrochemical stability and mechanical durability of BPMs under operational conditions, we investigated how fabrication conditions (including preconditioning, hot-pressing temperature and pressure, and catalyst loading) impact the adhesion of custom-made BPMs. T-peel studies were performed ex situ to quantify adhesive forces of BPMs, and bipolar membrane electrodialysis (BPMED) experiments were performed to assess the electrochemical performance of the corresponding BPMs. The results of this systematic comparison indicate that hydration and heated pressing create improved adhesion during the fabrication of BPMs, and BPMED testing shows that these fabrication techniques are not detrimental to the electrochemical performance of the BPMs.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Asymmetric Bipolar Membrane for High Current Density Electrodialysis Operation with Exceptional Stability

Bipolar membranes (BPMs) enable isolated acidic/alkaline regions in electrochemical devices, facilitating optimized environments for electrochemical separations and catalysis. For economic viability, BPMs must attain stable, high current density operation with low overpotentials in a freestanding configuration. We report an asymmetric, graphene oxide (GrOx)-catalyzed BPM capable of freestanding electrodialysis operation at 1 A cm–2 with overpotentials <250 mV. Use of a thin anion-exchange layer improves water transport while maintaining near unity Faradaic efficiency for acid and base generation. Voltage stability exceeding 1100 h with an average drift of 70 μV/h at 80 mA cm–2 and 100 h with an average drift of −300 μV/h at 500 mA cm–2 and implementation in an electrodialysis stack demonstrate real-world applicability. Continuum modeling reveals that water dissociation in GrOx BPMs is both catalyzed and electric-field enhanced, where low pK a moieties on GrOx enhance local electric fields and high pK a moieties serve as active sites for surface-catalyzed water dissociation. These results establish commercially viable BPM electrodialysis and provide fundamental insight to advance design of next-generation devices.

Lucas, Éowyn↗
DOE OSTI2025

Chemically Enhanced Electrodialysis (CEED) for Recovery of Rare Earth Elements

Rare-earth elements are crucial for numerous technologically relevant industries including energy, electronics, and aerospace; however, both the supply and separation of rare earths are pressing challenges. The long-term goal of the collaborative project is to develop a novel approach to existing extraction behaviors. To achieve this goal, a class of electrodialysis membranes with novel ion-gating functionality will be developed and paired with a conventional electrodialysis strategy. The hypothesis of the work is that incorporating sequestrants of suitable structures at the surface of the electrodialysis membrane will enhance extraction efficiency for ions of interest. Our ability to prepare sequestrants of diverse conformations and to adapt their molecular structure for binding lanthanides renders the proposed technology a versatile method for selective ion separation. Our approach will enable an entirely new technological approach to the separation of valuable rare-earth elements.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Electrodialysis: An effective methodology to purify the leachate of spent Li-ion batteries

The electrification of transportation and the transition of society towards low or net-zero carbon emissions has led to a skyrocketing global demand for Li-ion batteries. After a service life of three to ten years, Li-ion batteries have less than 80 % of their initial capacities and draw near to the end of their lives for practical utilization. Due to potential supply chain shortages and the value embodied in Li-ion batteries, it is imperative to recycle them, to recover the materials, and to improve the circularity and the sustinability of the industry. How to cost-effectively purify spent batteries while reducing time, energy, and waste emissions is a challenge faced by Li-ion battery recyclers. The first electrochemical membrane reactor reported in our group hasa high selectivity towards lower Cu 2+ , Al 3+ and Fe 3+ ions (<5 ppm) and retains >95% of the Ni 2+ , Co 2+ and Mn 2+ ions in the leachate. An advanced electrochemical membrane reactor was developed in this study. Further, not only does the new reactor have the same selectivity as the original reactor, but other advantages including a faster leachate processing rate (up to 10X faster). The advanced reactor can also directly generate acid at the anode side; eliminating the reactor restoration step. The prominent advantages that this electrodialysis technology has over chemical-precipitation methods include: (1) ion recovery efficiencies do not diminish after removing the impurities, Ni 2+ , Co 2+ and Mn 2+ , even at a higher initial Ni 2+ ion concentrations; in comparison, chemical precipitation has Ni 2+ , Co 2+ and Mn 2+ ion recovery efficiencies reduced significantly when the initial Ni 2+ , Co 2+ and Mn 2+ ion concentrations increase. (2) electrodialysis does not change the concentrations of Ni 2+ , Co 2+ and Mn 2+ ions significantly, but chemical precipitation could reduce Ni 2+ and Co 2+ ions to less than half of their initial values. Through electro-dialyzing the leachate, the H 2 evolution reaction mechanism was found to switch from the Volmer-acid Heyrovsky mechanism to the Volmer-alkaline Heyrovsky mechanism at a pH of around 3.7.

25 ENERGY STORAGE↗
DOE OSTI2022

Imidazolium-Type Anion Exchange Membranes for Improved Organic Acid Transport and Permselectivity in Electrodialysis

Most commercial anion exchange membranes (AEMs) deploy quaternary ammonium moieties. Alternative cation moieties have been explored in AEMs for fuel cells, but there are no studies focused examining alternative tethered cations in AEMs for ionic separations—such as organic acid anion transport via electrodialysis. H-cell and conductivity experiments demonstrate that tethered benzyl 1-methyl imidazolium groups in polysulfone AEMs enhance lactate conductivity by 49% and improved lactate anion flux by 24x when compared to a quaternary benzyl ammonium polysulfone AEM. An electrodialysis demonstration with the imidazolium-type AEM showed a 2x improvement in lactate anion flux and 20% improvement in permselectivity when benchmarked against the quaternary ammonium AEM. Molecular dynamics and 2D NOESY NMR revealed closer binding of lactate anions to the imidazolium cations when compared to the quaternary ammonium cation. It is posited that this closer binding is responsible to greater flux values observed with imidazolium-type AEM.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Evaluation of Electrodialysis Desalination Performance of Novel Bioinspired and Conventional Ion Exchange Membranes with Sodium Chloride Feed Solutions

Electrodialysis (ED) desalination performance of different conventional and laboratory-scale ion exchange membranes (IEMs) has been evaluated by many researchers, but most of these studies used their own sets of experimental parameters such as feed solution compositions and concentrations, superficial velocities of the process streams (diluate, concentrate, and electrode rinse), applied electrical voltages, and types of IEMs. Thus, direct comparison of ED desalination performance of different IEMs is virtually impossible. While the use of different conventional IEMs in ED has been reported, the use of bioinspired ion exchange membrane has not been reported yet. The goal of this study was to evaluate the ED desalination performance differences between novel laboratory‑scale bioinspired IEM and conventional IEMs by determining (i) limiting current density, (ii) current density, (iii) current efficiency, (iv) salinity reduction in diluate stream, (v) normalized specific energy consumption, and (vi) water flux by osmosis as a function of (a) initial concentration of NaCl feed solution (diluate and concentrate streams), (b) superficial velocity of feed solution, and (c) applied stack voltage per cell-pair of membranes. A laboratory‑scale single stage batch-recycle electrodialysis experimental apparatus was assembled with five cell‑pairs of IEMs with an active cross-sectional area of 7.84 cm2. In this study, seven combinations of IEMs (commercial and laboratory-made) were compared: (i) Neosepta AMX/CMX, (ii) PCA PCSA/PCSK, (iii) Fujifilm Type 1 AEM/CEM, (iv) SUEZ AR204SZRA/CR67HMR, (v) Ralex AMH-PES/CMH-PES, (vi) Neosepta AMX/Bare Polycarbonate membrane (Polycarb), and (vii) Neosepta AMX/Sandia novel bioinspired cation exchange membrane (SandiaCEM). ED desalination performance with the Sandia novel bioinspired cation exchange membrane (SandiaCEM) was found to be competitive with commercial Neosepta CMX cation exchange membrane.

42 ENGINEERING↗
DOE OSTI2025

Comparing Advanced Bipolar Membranes for High-Current Electrodialysis and Membrane Electrolysis

Advanced bipolar membranes (BPMs) with low water-dissociation overpotential (ηwd) may enable new electrochemical technologies for electrolysis, fuel cells, acid–base synthesis, brine remediation, lithium-battery recycling, and cement production. However, these advanced BPMs have only been demonstrated in BPM water electrolysis (BPMWE) configurations where the BPM is under static compression by the porous-transport layers. It is important to study these BPMs in applications like electrodialysis where large degrees of static compression are not possible. We present a BPM electrodialysis (BPMED) platform to measure water-dissociation overpotential (ηwd) and compare BPMWE and BPMED systems. We show advanced BPMs with half the ηwd compared to commercial BPMs for BPMED while maintaining ∼90% current efficiency from 0.05–0.5 A cm–2. The BPMED ηwd values are, however, about 0.2 V higher at 0.5 A cm–2 than those for BPMWE. Regardless, these results show that BPMs developed and optimized in BPMWE applications are well-suited for next-generation high-current-density BPMED technologies.

Vulpin, Olivia T↗
DOE OSTI2021

Ion-capture electrodialysis using multifunctional adsorptive membranes

Technologies that can efficiently purify nontraditional water sources are needed to meet rising global demand for clean water. Water treatment plants typically require a series of costly separation units to achieve desalination and the removal of toxic trace contaminants such as heavy metals and boron. We report a series of robust, selective, and tunable adsorptive membranes that feature porous aromatic framework nanoparticles embedded within ion exchange polymers and demonstrate their use in an efficient, one-step separation strategy termed ion-capture electrodialysis. This process uses electrodialysis configurations with adsorptive membranes to simultaneously desalinate complex water sources and capture diverse target solutes with negligible capture of competing ions. Our methods are applicable to the development of efficient and selective multifunctional separations that use adsorptive membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A Redox-Electrodialysis Model with Zero Fitting Parameters: Insights into Process Limitations, Design, and Material Interventions

Redox-Electrodialysis (r-ED) is an electrochemical desalination cell architecture that has recently received considerable interest, due to its low energy demand relative to electrochemical desalination technologies that rely on electrode-based ion removal. To further improve the energy efficiency of r-ED, we developed a lumped mathematical model with no adjustable parameters to investigate the various sources of overpotential within the cell. Existing models of electrodialysis and r-ED cells either do not accurately incorporate all phenomena contributing to the overpotential or utilize empirical fitting parameters. The model developed here indicates that ohmic overpotentials, especially in the diluate chamber, are the most significant contributors to energy losses. Based on this insight, we hypothesized that adding an ion exchange resin wafer in the diluate compartment would increase the ionic conductivity and decrease the energy demand. Experimental results showed an 18% reduction in specific energy use while achieving the same degree of salt removal (20 mM to 12 mM). Furthermore, the resin wafer enabled complete desalination to potable drinking levels at a current density previously unachievable within practical operating voltage limits (4.93 mA cm -2 ). We also expanded the model to explore differences in r-ED energy use between configurations using multiple cells and a single cell with increased area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A PRACTICAL ELECTRODIALYSIS MODEL FOR ACCELERATING SYSTEM DEVELOPMENT

Empirical optimization of electrodialysis (ED) is dependent on repetitive experiments with incremental adjustments, which is cost prohibitive at scale. While models can reduce the costs associated with optimization and scale-up, existing ED models are limited in application to specific use cases and tend to be developed for the exploration of specific transport phenomena. The field requires a practical system-level model, generalized for the broad range of ED systems. This work presents a modeling framework that enables rapid evaluation of membrane stack design, flow configuration, scale, and operational inputs. Across applications spanning 1 L to 5400 L; use of conventional and bipolar membranes; operation in continuous, batch and fed-batch modes; and feedstocks including seawater, brine, wastewater, and manure hydrolysate, the model achieves a mean R2 of 0.978 for concentration-time profiles and links design choices to techno-economic trade-offs, enabling cost-aware prioritization of system configurations.

Bipolar Membrane↗
DOE OSTI2025

Optimal design of power constrained bipolar membrane electrodialysis over a wide brine range

Bipolar membrane electrodialysis enables the in-situ production of high value products (e.g., acid and base) from clean brine, which is essential for a sustainable future. A technoeconomic assessment (TEA) was conducted on extraction of value from brine using the WaterTAP framework to identify optimal cost across a wide design space. Here, in the power constrained regime, increasing supplied salt concentration does not necessarily result in reduced cost or increased NaOH concentration. A detailed analysis elucidates the critical roles of water dissociation, limiting currents, and sodium diffusion play in shaping the landscape of levelized cost. Among these, water splitting predominantly influences the TEA outcomes across most of the optimal design space. Sensitivity analysis further demonstrates that membrane properties controlling water dissociation significantly impact the unit cost. The results indicate that innovations targeting improvements in water disassociation should be prioritised to effectively reduce the levelized cost of product production.

Bipolar membrane electrodialysis↗
DOE OSTI2025

Nonlinear programming optimization of a single-stack electrodialysis desalination system for cost efficiency

Electrodialysis (ED) presents a competitive method for desalinating brackish waters. In this work, we perform cost optimization of a single-stack ED system across a range of feed salinities and water recoveries while optimizing operating voltage, number of cell pairs, and cell length. The results of our optimization show that the levelized cost of water (LCOW) increases with an increase in feed salinity. The outcomes of our optimization show that cost-optimal design generally increases cell length while decreasing cell pair number and operating voltage with an increase in salinity. These trends are nonlinear, with the number of cell pairs and applied voltage exhibiting local maxima when operating at low salinity and high recovery. We discuss the underlying mechanism for cell length becoming a leveraging design parameter by inspecting the length-dependent profiles of key electrochemical properties of the ED cell. Finally, we present how increasing performance metrics and decreasing costs impact LCOW, demonstrating that innovations that decrease counter-current diffusion have resulted in the highest decrease of LCOW.

42 ENGINEERING↗
DOE OSTI2022

Electrodialysis through nafion membranes coated with polyelectrolyte multilayers yields >99% pure monovalent ions at high recoveries

Separation of monovalent and multivalent ions is important in processes ranging from water softening to recycling of Li. Previous studies show that cation-exchange membranes coated with multilayer polyelectrolyte films exhibit monovalent/divalent ion selectivities as high as 1000 in electrodialysis (ED) under ideal conditions with low ion recoveries. This work shows that even at 60-80% monovalent-ion recoveries, ED through Nafion membranes coated with protonated poly(allylamine)/poly(4-styrenesulfonate) multilayers can separate equimolar K + and Mg 2+ or Li + and Mg 2+ to give 99.5% pure monovalent ion. Moreover, the use of a low-volume receiving phase allows ED to concentrate the monovalent ion. Typical current efficiencies are around 70% for these separations. Selectivities appear to increase when the membrane-coating procedure uses a higher polyelectrolyte concentration in the deposition solution. Because the limiting current declines with ED time due to depletion of the monovalent ion in the source phase, use of a gradually decreasing applied current enhances current efficiency compared to ED at a constant high current. Further, the membranes also show Li + /Mg 2+ selectivities around 100 when Mg 2+ is in a 20-fold excess in the source phase at an ionic strength of 0.6 M, but selectivity decreases at even higher ionic strengths.

15 GEOTHERMAL ENERGY↗
DOE OSTI2020

Separation characteristics of cations and natural organic matter in electrodialysis

Natural organic matter (NOM) in water can cause the formation of disinfection byproducts (DBPs) when NOM reacts with a disinfectant such as chlorine. Nanofiltration (NF) and reverse osmosis (RO) are effective treatment methods to remove NOM. However, the simultaneous presence of both NOM and divalent cations such as Ca 2+ can enhance fouling in NF and RO. Therefore, an appropriate pretreatment to remove such cations before NF or RO would delay fouling and perhaps improve water recovery and NOM removal efficiency. Electrodialysis (ED) is potentially an excellent pretreatment method because it separates inorganic ions well using ion exchange membranes (IEMs) but does not separate NOM well because of its size and consequent low diffusivity. This research focused on ion and NOM separation with ED using three different types of commercially available IEM pairs, two different commercially available NOM sources, and six different influents at 500 mg/L total dissolved solids in the presence or absence of both hardness (Ca 2+ and Mg 2+ ) and NOM. The target waters of interest in this research were drinking water supplies that require little or no desalination but substantial removal of NOM; after NOM separation in NF or RO, some or all of the ED concentrate can be added to the NF/RO permeate to create the finished water prior to disinfection. The results indicate that ED can effectively separate alkaline earth metal ions without separation of NOM. Cation exchange membranes with high exchange capacity, high selectivity for divalent cations are desirable, and both anion and cation exchange membranes should have low affinity for organic adsorption. As a result, the process would work particularly well for NOM with relatively low hydrophobicity, since NOM adsorption to most surfaces increases with hydrophobicity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Effect of electrode rinse solutions on the electrodialysis of concentrated salts

The data presented indicate that modest attention to the chemistry of the electrode rinse solution can yield as much as 56% improvement in process efficiency. When operating electrodialysis (ED) with salt concentrations greater than 10,000 mg/l (as NaCl) the amperage can be relatively high even at low voltages. To maximize the overall rate of ion transport from diluate to concentrate, there is a need to minimize resistances in the electrode cells since these can represent as much as 30% of the total resistances in the entire process and in this particular ED unit, represented resistance roughly equivalent to that within the membrane stack. This work describes the performance of a 10-cell pair, 200 cm 2 (0.02 m 2 ) per membrane, pilot ED unit operated in batch mode at 5 V potential. The feedstock to the stack was varied from 0.5% to 6% NaCl. Results from Volt-amp profiles (2.0–15 V) were used as the rationale for choosing the preferred electrode rinse solution, 90 g/l (kg/m 3 ) disodium sulfate at pH 12.5. The recommended solution of 30 g/l (kg/m 3 ) disodium sulfate at neutral pH was tested against stronger solutions (60, 90, and 120 g/l (kg/m 3 ) disodium sulfate) at neutral pH and with 1 g/l (kg/m 3 ) sodium hydroxide added to yield solutions at pH 12.5. There were stark differences in the performance of the ED unit between the solutions at pH 7 and those at pH 12.5. The slopes of the Volt-amp profiles improved indicating less resistance to ion flow at pH 12.5. Most of the difference can be attributed to the greater conductivity of sodium hydroxide compared to disodium sulfate, where even a modest addition of 1 g/l (kg/m 3 ) sodium hydroxide increased the conductivity of the solution between 8 and 20% depending on the concentration of disodium sulfate. Most notably, the initiation voltage was 2.39 ± 0.08 V with solutions at pH 7 and 1.99 V ± 0.04 V when the rinse solutions were around pH 12.5, a difference of around 0.42 V. Since the full batch runs were performed at 5.0 V, this 0.42 V differential represented a loss of 8% in process efficiency. A series of tests showed a shift in initiation voltage occurred between pH 11.5 and 12.5. Nernst equations for water electrolysis are coupled with a simple flux model that estimates the concentration of hydroxide and hydronium ions at the electrode surfaces. This model indicates that the potential demanded by the electrodes is directly linked to the current. Furthermore, there is a steep drop in the potential demanded by the anode when there is sufficient hydroxide available to generate oxygen from hydroxide as opposed to generation from water. The voltage demand is minimal at pH 12.5 and reflective of the reference standard voltage (just over 1.23 V predicted at 0.1 amps). However, the flux model predicts that the voltage demanded by the electrodes at pH 7 is 1.61 V at 0.1 amps (the lowest amperage measurable with the power pack). In conclusion, comparing this result to the reference standard (E 0 = -1.23 V) yields a satisfactory explanation for the observed difference below reference standard of 0.42 V.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗