Desolvation Reaction Research Articles

Bio-Inspired Trace Hydroxyl-Rich Electrolyte Additives for High-Rate and Stable Zn-Ion Batteries at Low Temperatures.

High-rate and stable Zn-ion batteries working at low temperatures are highly desirable for practical applications, but are challenged by sluggish kinetics and severe corrosion. Herein, inspired by frost-resistant plants, we report trace hydroxyl-rich electrolyte additives that implement a dual remodeling effect for high-performance low-temperature Zn-ion batteries. The additive with high Zn absorbability not only remodels Zn2+ primary solvent shell by alternating H2 O molecules, but also forms a shielding layer thus remodeling the Zn surface, which effectively enhances fast Zn2+ de-solvation reaction kinetics and prohibits Zn anode corrosion. Taking trace α-D-glucose (αDG) as a demonstration, the electrolyte obtains a low freezing point of -55.3 °C, and the Zn//Zn cell can stably cycle for 2000 h at 5 mA cm-2 under -25 °C, with a high cumulative capacity of 5000 mAh cm-2 . A full battery that stably operates for 10000 cycles at -50 °C is also demonstrated.

LiPON/Multilayer-Graphene Interface Enables High-Rate Charging and Discharging

Graphite is the anode-active material commonly used in LIBs. In LIB, solid electrolyte interphase (SEI) is formed by the reduction of the liquid electrolyte, and the SEI plays a role as a passive film. In the charging process, Li ions transport in the liquid electrolyte and SEI, desolvation reactions of Li ions occur, and then Li ions insert into the graphite anode. It has been reported that the desolvation reaction of Li ions is the rate-limiting process[1]. Lithium phosphorous oxynitride glass (LiPON) is a well-known material as a solid electrolyte. However, it has been reported that the electrochemical window of LiPON ranges from 0.68 V to 2.63 V[2]. Therefore, it is possible that the decomposition reaction of LiPON occurs when the electrochemical cell is charged. Since the decomposition products can be a resistance, LiPON that is not easily reduced is required. In this study, we focused on the lithium phosphorus oxynitride glass (LiPON) electrolyte/multilayered graphene (MGr) film interface as an example without the desolvation process. In addition, we have investigated the relationship between LiPON composition ratio, electronic properties, and interfacial resistance by changing the sputtering conditions for LiPON film. Consequently, we found that the charge-transfer resistance at the MGr/LiPON interface was significantly small, although the MGr/LiPON interface was supposed to have inorganic solid electrolyte interphase resulting from the LiPON reduction decomposition. The figure shows a schematic illustration of the Liquid Electrolyte/MGr interface and the LiPON/MGr interface. Figure 1

Electrochemical Li+ Insertion/Extraction Reactions at LiPON/Epitaxial Graphene Interfaces.

Redox reactions of the Li+ insertion/extraction from one to two interlayers of graphene (Gr) on area-defined single-crystalline SiC substrates are investigated using lithium phosphorus oxynitride glass (LiPON) as the solid-state electrolyte. Unlike an organic liquid electrolyte, this glassy electrolyte does not induce a reduction current and excludes the desolvation reaction of Li+. Gr electrodes with less than two Gr layers show a single reduction peak and one or two oxidation peaks below +0.21 V (vs Li+/Li), differing distinctly from those of graphite and multilayer Gr, which display multiple peaks (multiple stage transitions). However, this finding aligns with the conventional understanding that graphite stage structure transitions proceed with stepwise increases or decreases in the number of Gr layers between adjacent Li-inserted interlayers. Cyclic voltammetry measurements indicate the presence of surface capacity due to Li+ adsorption/desorption at the LiPON/Gr interface. Moreover, Li+ insertion and extraction induce different charge transfer resistances at the level of a single interlayer. These sensitive measurements are achieved using high-quality epitaxial Gr and LiPON electrolyte, which prevent the formation of a solid electrolyte interphase and the desolvation reaction of Li+. Similar measurements using bilayer Gr produced by chemical vapor deposition coupled with a Gr transfer method and an ethylene carbonate/dimethyl carbonate liquid electrolyte are not reliable. Thus, the proposed method is effective for electrochemical measurement of Gr electrodes with a controlled number of layers.

Synthesis of α-AlH3 by organic liquid reduction method and its hydrogen desorption performance

Aluminum hydride (AlH3) is considered to be a promising hydrogen storage material due to its moderate dehydrogenation temperature and high hydrogen desorption capacity. However, AlH3 has multiple crystal forms, and it is difficult to prepare a single crystalline, which restricted the development of this material. In this study, a new organic liquid reduction method was used to prepare pure α-AlH3. The synthesis process includes two steps: primary reduction reaction in ether and subsequent desolvation reaction in toluene. The effects of reaction conditions on product composition were discussed in detail. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis were used to characterize the crystal structure and morphology of reaction products. Research results show that the final product is composed of α-AlH3 and γ-AlH3. The composition proportion of α-AlH3/γ-AlH3 can be adjusted by controlling reaction conditions. Through comparison and analysis, an optimal synthetic condition has been gained to obtain pure α-AlH3. The dehydrogenation performance of the obtained pure α-AlH3 were studied through thermal analysis methods. It is found that the α-AlH3 has a hydrogen desorption capacity of about 9.6 wt% below 200 °C. The dehydrogenation activation energy was also evaluated by using Kissinger and Friedman methods. This study provides a more simple and efficient method for synthesising pure α-AlH3, and also offers some reference for the future research of AlH3.

Structure-property relations of lightweight Ti-Sc-Zr-Nb-V high-entropy alloys

Recently, it has been a hot topic to explore lightweight high entropy alloys (HEAs) for their future potential application as engineering materials. In this work, novel lightweight Ti 22 Sc 22 Zr 22 Nb 17 V 17 , Ti 24 Sc 20 Zr 22 Nb 17 V 17 , Ti 24 Sc 22 Zr 20 Nb 17 V 17 , and Ti 26 Sc 20 Zr 20 Nb 17 V 17 HEAs were fabricated by rapid solidification. The phase constituents and microstructures of the HEAs in the cast and annealed states were characterized by X-ray diffraction spectrum (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), and energy dispersive spectrum (EDS), while their mechanical properties were also investigated in detail. The microstructures of the cast samples consist of the coarse equiaxed BCC dendrites with extremely heterogeneous chemical distributions and the intergranular structures that are made up of BCC and HCP precipitates. Both precipitates inside the intergranular structures exhibit slightly large worm-shaped and fine lamellar morphology features. After annealing at temperatures below 1273 K, the desolvation reaction occurs due to the strong solute redistribution, leading to the disappearance of the lamellar structures, the coarsening of the large worm-shaped BCC particles, and the solid phase separation of the equiaxed BCC dendrites. At 1273 K, the combined interaction from the eutectoid transformation and phase separation leads to the formation of the TiNbV-rich BCC, ScZr-rich HCP, and transitional BCC+HCP structures. Compared with reported lightweight HEAs (density ≤ 6.5 g/cm 3 ), the present HEAs in the cast and annealed states exhibit excellent comprehensive mechanical properties, which are attributed to the combined effect from the solid-solution strengthening, second phase strengthening, and fine-grained strengthening. The present studies provide potential candidates as lightweight high-temperature structural materials in the future. • Compositional variations and heat treatments on structure and properties of as-cast lightweight HEAs were investigated. • Phase types are well consistent with the calculation prediction. • Dendritic intergranular regions contain some worm-shaped and fine lamellar BCC particles and HCP precipitates. • Low-temperature annealing induces strong solute redistribution within BCC and HCP phases. • Annealing at 1273 K induces the eutectoid transformation and phase separation.

Thermo Gravimetric analysis of Vetiveria zizanioides /Jute/Glass fiber reinforced hybrid polymeric composites

Abstract An investigation has been made to predict the effects of thermo gravimetric analysis on developed hybrid composites to find the thermal stability along with the water retention and chemical resistance. Thermogravimetric analysis (TGA) is an analysis of physical and chemical change in the properties of materials. The change of properties is function of temperature with heating rate as constant), or as a function of time (with constant temperature and/or constant mass loss).It provides information about physical phenomena, such as second-order phase transitions, along with characteristics like desorption, sublimation, absorption, and vaporisation. Likewise also provides information about some chemical phenomena including chemisorptions, desolvation (especially dehydration), decomposition and solid-gas reactions. It is observed that, the inclusion of natural fibre improves thermal properties of any composite materials..

Three-dimensional lithium mapping of graphite anode using laser-induced breakdown spectroscopy

Herein, a method has been described to rapidly obtain a semi-quantitative three-dimensional lithium distribution of a lithium-ion battery graphite anode using laser-induced breakdown spectroscopy (LIBS) measurements. LIBS measurements of the graphite anodes with a diameter of 10 mm were performed in an argon atmosphere of 1000 Pa until the depth of 150 μm using the Li emission line of 610.4 nm. The emission intensity was measured for the pitch of 500 μm in plane. Homogeneous and inhomogeneous lithium distributions were observed in the anodes after both charge and charge-discharge processes. The inhomogeneous lithium distribution after the charge process was attributed to the preferentially reacted area in the anode, while that after the charge-discharge process was likely related to the low desolvation reaction rate of lithium ions at the solid electrolyte interphase. These inhomogeneous lithium distributions were consistent with the results from the charge-discharge curves and the lithium ion transfer mechanism. Thus, it was proven that it is possible to acquire a three-dimensional lithium distribution of a graphite anode of a lithium-ion battery by LIBS measurements.

In Vitro transdermal delivery of sesamol using oleic acid chemically-modified gelatin nanoparticles as a potential breast cancer medication

In this study, gelatin was conjugated to oleic acid, a known skin penetration enhancer, by means of an amidation reaction. The reaction was performed in the presence of carbodiimide/N-hydroxysuccinimide as activators in order to form a gelatin oleic acid conjugate. The successful synthesis of this conjugate was confirmed by FTIR and 1H NMR. Moreover, oleic-acid conjugated nanoparticles were prepared by the single desolvation reaction. Sesamol, a natural anticancer drug, was loaded into the nanoparticles in-process. A small particle size of 185 nm ± 2.6, low PDI (0.0365 ± 0.0165) and relatively high entrapment efficiency (44.6% ± 3.8) associated with a drug loading approaching 2.23 mg ± 0.19 were achieved. The in vitro release of sesamol from the newly developed system compared to the sesamol solution was assessed. In vitro Permeation of sesamol was performed through albino mice skin using a newly developed UPLC-MS/MS method where the oleic acid-conjugated gelatin nanoparticles demonstrated the best permeation results. Cytotoxicity studies on MCF-7 breast cancer cells were performed where the newly developed nanoparticles scored the lowest IC50 of 595 μM ± 32.3. As a conclusion, the newly developed system was successful in the transdermal delivery of sesamol and the cytotoxicity of the new formulations was confirmed.

Preparation and Characterization of Hybrid Solid Electrolyte Consisted of Li Conductive Polyethylene Oxide and Inorganic Electrolyte Li7La3Zr2O12

All-solid-state lithium battery, which has higher energy density and safety than conventional lithium ion batteries are desired to stationary storage battery and electric vehicle battery. Solid polymer electrolyte (SPE) are one of candidate materials for all-solid-state lithium battery in term of high flexibility, compact, and the ability to prevent lithium dendrite formation.[1-2] Li7La3Zr2O12(LLZO) with garnet structure is most representive oxide-based inorganic electrolyte. and suitable stability for lithium metal anodes. Representive crystal structure of LLZO is reported cubic structure and tetragonal structure. Cubic LLZO shows relatively high ionic conductivity (10-4~10-3[S cm-1] ) at room temperature in oxide-based inorganic elctrolyte. Ionic conductivity of tetragonal phase is about 2 orders of magnitude lower than that for the cubic phase.[3-4] In this study, we prepared polyether-based polymer-LLZO composite electrolyte and measured temperature dependence of bulk ionic conductivity, interfacial resistance of Li/electrolyte and glass transition temperature (T g ) used by AC impedance method and differential scaning calorimetry (DSC). We investigated that the influence of LLZO additions for ionic conduction and thermal property by hybridization of LLZO and polyether-based solid polymer electrolyte. Experimental Preparation and characterization of hybrid solid electrolyte film Preparation of sample and cell preparation were examined in Ar-filled grovebox. LiTFSA was dissolved in polyether-based macromonomer solution ([Li] / [O] =0.1, amount of O was based on oxide unit from polyether). Tetragonal Li7La3Zr2O12 1.0wt% and 5.0wt%, DMPA (photoinitiator) and acetonitrile were added to the solution and stirred by stirrer. The solution was dried over 10h and obtained complete homogenerous solution. The solution was casted on glass plate and covered by two glass plate and 0.5mm teflon spacer. Hybrid solid electrolyte films were fabricated by radical photo polymerization under UV irradiation at 5 min. Characterization of hybrid solid electrolyte Ionic conductivity of hybrid solid electrolyte were measured by AC impedance method. Measurement samples were 12mm diameter disk. Frequence range is from 100kHz to 10mHz with a 500mV amplitude. Temperature range is -30 to 80 and all samples were thermally equilibrated at each temperature at least 1.5 h prior to the measurement. T g of hybrid solid electrolytes were measured by DSC measurement. The hybrid solid electrolyte films were cut into circle of 3mm diameter and enclosed into Al pans in the Ar-filled glovebox. The DSC measurements of hybrid solid electrolyte were conducted with the samples cooling to -100, followed by heating to 150 at cooling and heating rate of 10/min. The hybrid solid electrolyte films were cut into circle of 19mm diameter and then were sandwiched between Li metal nonblocking electrodes. These samples were enclosed into 2032 coin cell completely. Coin cells were settled in a constant temperature chamber at 60 over 100h to stabilize interface of Li/hybrid solid electrolyte. After that, temperature dependence of interfacial resistance of Li/hybrid solid electrolyte were mesured by AC impedance method under the same condition of ionic conductivity measurement. Results and discussion Fig.1 shows the temperature dependences of ionic conductivity for hybrid electrolyte. Ionic conductivity of the hybrid solid electrolyte showed larger values than that of LLZO free electrolyte. This tendency was remarkable in the case of low temperature. Fig. 2 shows DSC thermograms of hybrid solid electrolyte. T g of hybrid solid electrolyte were lower than LLZO free system. It is assumed that local segment motion of polymer were improved by interaction of between LLZO and matrix in polymer. Fig.3 shows temperature dependence of interfacial resistance of Li/hybrid solid electrolyte. Interfacial resistance of hybrid solid electrolyte composited 5.0wt% LLZO was lower than LLZO free system. It is assumed that solvation and desolvation reaction was promoted at Li/electrolyte interface by improving of local segment motion in matrix.

Mechanochemical Synthesis of Multicomponent Crystals: One Liquid for One Polymorph? A Myth to Dispel

Identifying as many polymorphs as possible for a molecular compound is important in the design of materials with desired properties. In this paper we demonstrate, using a simple experimental procedure, how the amount of liquid present during liquid-assisted mechanochemical reactions can be used to rapidly explore polymorph diversity. Through detailed experimental evidence it is concluded that for the specific (multicomponent) crystal system investigated (caffeine–anthranilic acid) the commonly accepted rule “one liquid for one specific polymorph” is not correct. Additionally we demonstrate that through modification of the amount of added liquid it is possible to form a polymorph previously obtained only by a desolvation reaction. We believe that while the results raise many mechanistic questions the approach is advantageous as a means of rapidly screening for polymorph diversity as well as being a simple screening methodology. While we focus here on a cocrystal system, we believe a similar approach will b...

Crystallization of dicalcium phosphate dihydrate with presence of glutamic acid and arginine at 37 °C.

The formations of non-metabolic stones, bones and teeth were seriously related to the morphology, size and surface reactivity of dicalcium phosphate dihydrate (DCPD). Herein, a facile biomimetic mineralization method with presence of glutamic acid and arginine was employed to fabricate DCPD with well-defined morphology and adjustable crystallite size. In reaction solution containing more arginine, crystallization of DCPD occurred with faster rate of nucleation and higher density of stacked layers due to the generation of more OH(-) ions after hydrolysis of arginine at 37 °C. With addition of fluorescein or acetone, the consumption of OH(-) ions or desolvation reaction of Ca(2+) ions was modulated, which resulted in the fabrication of DCPD with adjustable crystallite sizes and densities of stacked layers. In comparison with fluorescein-loading DCPD, dicalcium phosphate anhydrate was prepared with enhanced photoluminescence properties due to the reduction of self-quenching effect and regular arrangement of encapsulated fluorescein molecules. With addition of more acetone, DCPD was prepared with smaller crystallite size via antisolvent crystallization. The simulated process with addition of amino acids under 37 °C would shed light on the dynamic process of biomineralization for calcium phosphate compounds.

New Solvates of an Old Drug Compound (Phenobarbital): Structure and Stability

The solvent formation of phenobarbital, an important drug compound with an unusually complex polymorphic behavior, was studied in detail. Monosolvates with acetonitrile, nitromethane, dichloromethane, and 1,4-dioxane were produced and characterized by single-crystal and powder X-ray diffraction, thermoanalytical methods, FT-IR, Raman, and solid-state NMR spectroscopy. Thermal desolvation of these compounds yields mainly mixtures of polymorphs III, II, and I. At a low relative humidity (25 °C) the solvates transform to polymorph III, and at higher relative humidity the monohydrate and the metastable polymorphs IV and VI can be present as additional desolvation products. These results highlight the potential complexity of desolvation reactions and illustrate that a tight control of ambient conditions is a prerequisite for the production of phase-pure raw materials of drug compounds. Transformation in aqueous media results in the monohydrate. Below room temperature, the 1,4-dioxane monosolvate undergoes a reversible single-crystal-to-single-crystal phase transition due to the ordering/disordering of 50% of its solvent molecules. Dipolar-dephasing NMR experiments show that the solvent molecules are relatively mobile. Deuterium NMR spectra reinforce that conclusion for the dioxane solvent molecules. The crystal structure of an elusive 1,4-dioxane hemisolvate was also determined. This study clearly indicates the existence of "transient solvates" of phenobarbital. The formation of unstable phases of this kind must be considered in order to better understand how different solvents affect the crystallization of specific polymorphs.

In-situ Fourier transform infrared spectroscopic analysis on dynamic behavior of electrolyte solution on LiFePO4 cathode

The dynamic behavior of 1.0 mol dm−3 LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) mixed solvent (1:1 in volume) on lithium iron phosphate (LiFePO4) thin film electrode fabricated by RF-sputtering was investigated by in-situ Fourier transform infrared (FT-IR) spectroscopy. The solvation and desolvation reactions of EC and DEC with Li+ ion were observed in the charge and discharge processes of thin film electrode, respectively. In addition, the adsorption of solvent molecules on the electrode surface was suggested by polarized IR analyses. Lithium alkylcarbonate, lithium carboxylate and lithium carbonate were formed as decomposition products of the electrolyte solution at the anodic potential more than 4.5 V vs. Li/Li+.

Inclusion compounds of hydroxynaphthoic acids: co-crystal vs. salt formation

6-Hydroxy-2-naphthoic acid, H1, forms solvates with 1,4-dioxane (DIOX) and dimethyl sulfoxide (DMSO), and their structures are stabilized by host–host and host–guest hydrogen bonds. H1 forms a hydrated salt with 1,4-diazabicyclo[2.2.2]octane, DABCO, with stoichiometry 2H1·2DABCO·3H2O. Two other naphthoic acid isomers, 1-hydroxy-2-naphthoic acid, H2, and 3-hydroxy-2-naphthoic acid, H3, form salts with DABCO with host : guest ratios of 2 : 1. The kinetics of thermal decomposition of the H1·½DIOX compound yields an activation energy of ∼60 kJ mol−1 for the desolvation reaction.

Investigations on the Desolvation Reaction of Pseudopolymorphic Forms of Hydrocortisone

The crystal structures of two pseudopolymorphic modifications of the glucocorticoid hydrocortisone were determined, in addition to the known structures of the 2-propanol (1), methanol (2) and pyridine (3) solvate reported recently. The chloroform solvate (4) and the N,N′-dimethylformamide solvate (5) crystallize in the monoclinic space group P21, with a = 12.5947 (8) A, b = 12.4413 (5) A, c = 14.9884 (11) A, β =90.571 (9)°, V = 2348.5(2) A3 for (4) and a = 13.4186 (10) A, b = 6.0878 (3) A, c = 14.6595 (11) A, β = 104.711 (10)°, V = 1158.27(14) A3 for 5. The crystal structures of 1, 3, and 5 are isotypic and are very similar to that of the thermodynamically metastable solvent free modification III of hydrocortisone. The removal of solvents from the pseudopolymorphic forms at elevated temperatures results in the formation of the thermodynamically most stable form I or the metastable form II of hydrocortisone. For the methanol solvate, the desolvation reaction indicates the formation of a new modification of...

Desolvation Kinetics of Sulfameter Solvates

Solvates are often encountered in pharmaceutical solids and knowledge of their physical stability is necessary for their effective formulation. This work investigates the solid-state stability of five structurally related solvates of sulfameter (5-methoxysulfadiazine) by studying the kinetics of their desolvation reaction with thermogravimetric analysis, both isothermally and nonisothermally. Desolvation kinetic analysis was done isothermally by conventional model-fitting and nonisothermally by the complementary method. Calculated kinetic parameters (model, A and Ea) were compared and related to the crystal structure of these solvates. A relationship was established between desolvation activation energy from isothermal results and solvent size; the larger the solvent molecule, the higher its solvate's desolvation activation energy. The best fitting solid-state reaction model correlated to single crystal structural features of sulfameter-solvates where solvent molecules occupied cavities in the unit cell. Finally, it was found that kinetic parameters obtained isothermally and nonisothermally were at variance. Therefore, kinetic results obtained from one method may not be extended to results form the other.

Thermal properties of AlH 3-etherate and its desolvation reaction into AlH 3

Thermal properties of AlH 3-etherate and its desolvation reaction into AlH 3 were experimentally investigated under heating and isothermal processes. AlH 3-ehterate was desolvated to γ-AlH 3 which immediately transformed into α-AlH 3 in the heating process. The results under the isothermal process provide appropriate conditions to effectively obtain α- and γ-AlH 3 by restraining the occurrence of the dehydriding reaction into metallic Al.

Thermodynamic properties of the molecular complexes of C60with monosubstituted naphthalenes

The binary systems of C60with α-methyl- and α-chloronaphthalene have been studied by means of differential scanning calorimetry. C60was found to form the molecular complex of the van der Waals type with α-methylnaphthalene which melts incongruently below the boiling point of the solvent at temperature 382.7±3.0 K. The enthalpy of the desolvation reaction is 14.1±0.5 kJ mol-1of C60. The molar ratio of fullerene to solvent in the solvate is 1:1.5. In the system C60-α-chloronaphthalene a two-stage incongruent melting process has been observed at temperatures 314.1±4.6 K and 375.7±7.4 K with the enthalpies 8.1±2.6 kJ mol-1and 11.6±1.0 kJ mol-1, respectively. The composition of the most solvated phase equilibrated with the saturated solution at room temperature and below the first of the incongruent melting transitions was determined as 1:1.5. Based on the results obtained the thermodynamic characteristics of the incongruent melting reactions have been revealed and influence of solvate formation on solubility of C60has been discussed.

Complementary Use of Model-Free and Modelistic Methods in the Analysis of Solid-State Kinetics

There are many methods for analyzing solid-state kinetic data. They are generally grouped into two categories, model-fitting and isoconversional (model-free) methods. Historically, model-fitting methods were widely used because of their ability to directly determine the kinetic triplet (i.e., frequency factor [A], activation energy [E(a)], and model). However, these methods suffer from several problems among which is their inability to uniquely determine the reaction model. This has led to the decline of these methods in favor of isoconversional methods that evaluate kinetics without modelistic assumptions. This work proposes an approach that combines the power of isoconversional methods with model-fitting methods. It is based on using isoconversional methods instead of traditional statistical fitting methods to select the reaction model. Once a reaction model has been selected, the activation energy and frequency factor can be determined for that model. This approach was investigated for simulated and real experimental data for desolvation reactions of sulfameter solvates.

Blackbody Infrared Radiative Dissociation of Partially Solvated Mixed Ligand Ru(II) Complex Ions

Unimolecular dissociation reactions of gas-phase partially solvated transition metal complex ions, diamminebis(2,2‘-bipyridine)ruthenium(II), [Ru(NH3)2(bipy)2]2+, tetraammine(2,2‘-bipyridine)ruthenium(II), [Ru(NH3)4bipy]2+, and pentaammine(2-methylpyrazine)ruthenium(II), [Ru(NH3)5MePyz]3+, have been investigated with electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI−FTICR/MS) under low pressure (<10-8 mbar) conditions. Under these conditions, dissociation of solvent from the complex ions is driven primarily by absorption of blackbody photons from the FTICR analyzer cell walls, that is, via blackbody infrared radiative dissociation (BIRD), with little collisional contribution at pressures below 10-8 mbar. The replacement of ammine hydrogens with deuterium increases measured BIRD rate constants. Optimized geometries, vibrational frequencies, and IR absorption band intensities have been calculated for the complexes by semiempirical and ab initio methods. These calculated parameters have been employed in master equation modeling of the desolvation reactions to extract dissociation energetics. Solvation energies obtained by master equation modeling were found to be in the range 19 ± 1 kcal/mol for the dissociation of acetone from various mixed ligand Ru(II) complex ions studied in this work. This is about 4 kcal/mol higher than for the comparable complexes containing only bipyridyl ligands and no ammine ligands.