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This review article summarizes the reported crystallographically determined structures of compounds containing a hydrated metal ion and the reported structures of hydrated metal ions in aqueous solution. A short overview of the methods available to study structures of metal complexes in solution is given.

The use of bismuth in the society has steadily increased during the last decades, both as a substitute for lead in hunting ammunition and various metallurgical applications, as well as in a range of consumer products. At the same time, the environmental behavior of bismuth is largely unknown. Here, the binding of bismuth(III) to organic soil material was investigated using extended X-ray absorption spectroscopy (EXAFS) and batch experiments. Moreover, the capacity of suwannee river fulvic acid (SRFA) to enhance the solubility of metallic bismuth was studied in a long-term (2 years) equilibration experiment. Bismuth(III) formed exceptionally strong complexes with the organic soil material, where >99% of the added bismuth(III) was bound by the solid phase, even at pH 1.2. EXAFS data suggest that bismuth(III) was bound to soil organic matter as a dimeric Bi3+ complex where one carboxylate bridges two Bi3+ ions, resulting in a unique structural stability. The strong binding to natural organic matter was verified for SRFA, dissolving 16.5 mmol Bi per gram carbon, which largely exceeds the carboxylic acid group density of this compound. Our study shows that bismuth(III) will most likely be associated with natural organic matter in soils, sediments, and waters.

The deliverances of our conscience are heartfelt, but not necessarily reason-based, moral convictions that concern our own behaviour. The fact that conscientious objections to a regulation, like a prohibition or obligation, express a heartfelt conviction that it is morally wrong to comply or morally permissible not to comply with the regulation provides a moral reason to respect the conviction because failing to do so is likely to cause objectors considerable suffering. But for conscientious objections to succeed in justifying exempting objectors from complying with the regulation, the suffering caused by forcing compliance must outweigh the suffering produced by exempting them from compliance. In the case of obligations, this necessitates that others with a similar competence are available to replace them. Conscientious objectors can never justifiably demand to be granted exemptions. This takes acts of generosity made feasible by favourable circumstances, such as the availability of replacements.

Solid titanium phosphate, TiP, materials hold great promise for wastewater treatment for removal of metal ions and complexes. A series of TiP materials, synthesised at mild conditions and short reaction times, have been structurally characterised using solid-state X-ray absorption spectroscopy, phosphorus and titanium K edge XANES and EXAFS, and P-31 and Ti-47/49 NMR spectroscopy. The titanium K edge EXAFS data of alpha-Ti(HPO4)(2)center dot H2O (alpha-TiP) revealed octahedral coordination of oxygens around titanium. Repeated washing of primary beta-/gamma-TiP with hydrochloric acid results in formation of a weakly ordered solid, TiO(OH)(H2PO4)center dot H2O, TiP1-H. The structure of TiP1-H is shown by Ti EXAFS to be a titanyl compound, containing a short Ti=O bond. The analogous data for linked titanium phosphate compounds (LTP) disclosed that inter-linkage occurs between alpha-TiP and titanyl phosphate units, supported by P-31-P-31 NOESY NMR data. Ti-47/49 NMR and Ti pre-edge XANES show evidence of two different titanium environments in LTP, one very similar to that observed in TiP1-H and a second more symmetric octahedral environment. Data are discussed in terms of induced acidic hydrolyses of titanium(IV) and phosphate counterpart during washings with hydrochloric acid and water. A straightforward relation between synthesis parameters/post synthetic treatment and structural re-arrangement in the materials is established.

Solid-state intercalation was applied to prepare organo-smectites using cationic surfactants and natural clays containing smectite at various surfactant/smectite ratios. The surfactants enter the interlayers of smectites causing a swelling of the clays. The used clays were collected in Siétougou and Diabari villages located in the eastern part of Burkina Faso. The solid-state intercalation was successful for all four surfactants applied, n-dodecyltrimethylammonium bromide, (n-C12H25(CH3)3NBr), n-tetradecyltrimethylammonium bromide, (n-C14H29(CH3)3NBr), n-hexadecyltrimethylammonium bromide (n-C16H33(CH3)3NBr) and di-n-dodecyldimethyl­ammonium bromide ((n-C12H25)2(CH3)2NBr) at different levels of the cation exchange capacity (CEC). The synthesized organo-smectites were characterized regarding relative density, structural and textural properties. XRPD data showed a systematic increase of the basal spacing of the unit cell of the smectite up to >38 Å at 2.0-CEC loading of the surfactant. This increase indicates that the surfactants penetrated into the smectite interlayers with the surfactants being arranged parallel to the layers at low concentrations and almost perpendicular at high ones. FTIR spectra of the organo-smectites showed a decrease in the intensities of the water bands at around 1630 cm-1 and 3400 cm-1, and new specific bands close to 2920 cm-1 and 2850 cm-1 were assigned to the asymmetric and symmetric stretching of CH2 groups of the surfactants, respectively. KEY WORDS: Smectite, Organo-smectite, Surfactant, Intercalation Bull. Chem. Soc. Ethiop. 2021, 35(1), 43-59. DOI: https://dx.doi.org/10.4314/bcse.v35i1.4

In the present study the solution and coordination chemistry of copper(II)–alkyl-N-iminodiacetate systems are studied in aqueous solution by potentiometry, using ion selective copper and pH electrodes, EXAFS (extended X-ray absorption fine structure) and dye probe molecular absorption spectrophotometry. Alkyl-N-iminodiacetates with varying alkyl chain length, methyl (CH3–), n-hexyl (C6H13–), n-dodecyl (C12H25–) and n-octadecyl (C18H37–) were used to tune the amphiphilic properties of the ligands. The polar head groups have both oxygen (hard Lewis base) and nitrogen donor (border-line Lewis base) atoms. This means that metal ions with different bonding characteristics may bind these ligands differently. Furthermore, the chelating properties of the polar head group may be regulated by pH as the acid–base properties of the imine and carboxylic acid groups are different. Copper(II) forms two stable complexes with alkyl-N-iminodiacetates with short alkyl chains, present as monomers in aqueous solution, log10β1 = 11.10(2), log10β2 = 19.5(2) for methyl-N-iminodiacetate, and log10β1 = 12.22(4), log10β2 = 21.9(2) for n-hexyl-N-iminodiacetate. n-Octadecyl-N-iminodiacetic acid, present as large aggregates in acidic aqueous solution, has short strong hydrogen bonds between carboxylic acid and carboxylate groups in the surface of the aggregates, which hinder complex formation at pH values below 4, obstructs it in the pH region 4–7, while the complex formation behaves as for short-chained alkyl-N-iminodiacetates at pH > 7. The structure around copper in copper(II)–alkyl-N-iminodiacetate complexes in aqueous solution and solid state formed at different pH values and copper(II):alkyl-N-iminodiacetate ratios has been determined by EXAFS. The coordination chemistry of copper(II) shows four strong bonds in the equatorial plane, and two different Cu–O/N bond distances, ca. 0.2 Å apart, in the axial positions of a non-centrosymmetric tetragonally elongated octahedron.

ACS catalysis 11(5), 2999 - 3008 (2021). doi:10.1021/acscatal.0c04374, A well-studied heterogeneous palladium(II) catalyst used for the cycloisomerization of acetylenic acids is known to be susceptible to deactivation through reduction. To gain a deeper understanding of this deactivation process and to enable the design of a reactivation strategy, in situ X-ray absorption spectroscopy (XAS) was used. With this technique, changes in the palladium oxidation state and coordination environment could be studied in close detail, which provided experimental evidence that the deactivation was primarily caused by triethylamine-promoted reduction of palladium(II) to metallic palladium nanoparticles. Furthermore, it was observed that the choice of the acetylenic acid substrate influenced the distribution between palladium(II) and palladium(0) species in the heterogeneous catalyst after the reaction. From the mechanistic insight gained through XAS, an improved catalytic protocol was developed that did not suffer from deactivation and allowed for more efficient recycling of the catalyst., Published by ACS, Washington, DC

Removal of metal compounds from wastewater using processes where metals can be removed and valuable chemicals recycled is of significant industrial importance. Chelating surfactants are an interesting group of chemicals to be used in such applications. Carboxylated polyamines are a promising group to be used in such processes. To apply carboxylated polyamines as chelating surfactants, detailed knowledge of the solution chemistry, including complex formation, kinetics and structures of pure fundamental systems, is required. In this study zinc(II) alkyl-N-iminodiacetate systems with varying length of the alkyl chain have been studied. Acidic and stability constants have been studied by potentiometry, and the structures of both solids and aqueous solutions have been determined by EXAFS. Zinc(II) forms two strong complexes with alkyl-N-iminodiacetates in aqueous solution. In an attempt to determine the acidic constants of these complexes, the deprotonation of the nitrogen atom in the complex bound ligands, it was observed that this reaction is very slow and no accurate values could be obtained. The bis(alkyl-N-iminodiacetato)zincate(II) complexes take, however, up two protons in the pH region 3–7, which means that this complex is approximately singly protonated in the pH region 3–7 and doubly protonated at pH n-hexyl-N-iminodiacetato)zincate(II) complex at pH = 13 has a distorted octahedral configuration with four short strong Zn–O bonds at 2.08(1) Å, while the Zn–N bonds are weaker at much longer distance, 2.28(2) Å. Similar configurations are also found in most reported structures of zinc(II) complexes with carboxylated amines/polyamines. The singly protonated complex seems to be five-coordinate, with four Zn–O bond distances at ca. 2.03 Å, and a single Zn–N bond distance in the range 2.15–2.25 Å. The relationship between the structure of the protonated bis(n-hexyl-N-iminodiacetato)zincate(II) complex and the slow kinetics in the region pH = 3–7 are discussed.

The strength of hydrogen bonding to and structure of hydrated oxometallate ions in aqueous solution have been studied by double difference infrared (DDIR) spectroscopy and large-angle X-ray scattering (LAXS), respectively. Anions are hydrated by accepting hydrogen bonds from the hydrating water molecules. The oxygen atom of the permanganate and perrhenate ions form weaker and longer hydrogen bonds to water than the hydrogen bonds in bulk water (i.e., they act as structure breakers), while the oxygen atoms of the chromate, dichromate, molybdate, tungstate, and hydrogenvanadate ions form hydrogen bonds stronger than those in bulk water (i.e., they act as structure makers). The oxometallate ions form one hydration shell distinguishable from bulk water as determined by DDIR spectroscopy and LAXS. The hydration of oxoanions results in X–O bond distances ca. 0.02 Å longer than those in unsolvated ions in the solid state not involved in strong bonding to counterions. The oxygens of oxoanions with a central atom from the second and third series in the periodic table and the hydrogenvanadate ion hydrogen bind three hydrating water molecules, while oxygens of oxoanions with a heavier central atom only form hydrogen bonds to two water molecules., The strength of the hydrogen bonding to and the structure of hydrated oxometallate ions in aqueous solution have been studied by double difference infrared spectroscopy and large-angle X-ray scattering, respectively.

This paper clarifies and defends against criticism our argument in Unfit for the Future that there is no moral right to privacy. A right to privacy is conceived as a right that others do not acquire information about us that we reserve for ourselves and selected others. Information acquisition itself is distinguished from the means used to acquire it and the uses to which the information is put. To acquire information is not an action; it is to be caused to be in an internal state. By contrast, means of acquisition and uses of information are actions that can be voluntarily controlled. We can therefore have rights against others that they stay away from certain means and uses but not from information acquisition in itself. An omniscient, omnipotent and omnibeneficient being is not thought to violate a right to privacy because its means and uses of information are morally acceptable.

Contrary to Schopenhauer’s claim that positive feelings consist simply in the cessation of negative feelings, it is contended that positive feelings are feelings just like negative feelings. But there is a bias or asymmetry in favour of the negative to the effect that negative feelings can in general have a greater intensity: pain can be more intense than pleasure, depression than elation, etc. This is because negative feelings often signal losses that are irreversible, and that by themselves guarantee reductions of well-being, whereas this is not true of the improvements signalled by positive feelings. Due to this asymmetry, compassion can be stronger than sympathetic joy and, as these emotions provide moral reasons, this explains why, intuitively, it seems morally more urgent to prevent what is bad than to produce what is good as, e.g. negative utilitarianism maintains.

Paul Bloom and Jesse Prinz have argued that empathy is a poor guide to morality because it is partial, focused on individuals who are near and dear to us, present before our senses, and similar to us, etc. It is here conceded that this is true of spontaneous empathy, but that empathy can be voluntarily controlled and reflective because it consists in imagining what somebody else than ourselves at present is feeling. This means that we can counteract the partiality of our spontaneous empathy, though it is exceedingly difficult to overcome all partiality which is necessary for the kind of universal compassion envisaged by Schopenhauer. In this chapter an attempt is also made to make sense of his conception of the relation between such compassion and ascetic self-renunciation.

According to Arthur Schopenhauer, compassion is the basis of morality. He sees concern for justice as a negative form of compassion, directed at not harming anyone, as opposed to the more far-reaching, positive form of benefiting. He thinks a higher degree of compassion involves realizing that the spatio-temporal separation of individuals is illusory and that in reality they are all identical. Such compassion is impartial and all-encompassing. Compassion is suited to be the centre of morality because its object are negative feelings, and only these are real. Contrary to these Schopenhauerian claims, it is here argued that compassion must be supplemented with attitudes like sympathy and benevolence because positive feelings exist alongside negative feelings; that a concern for justice, though morally essential, is independent of these attitudes which are based on empathy; that these attitudes involve not identifying oneself with others, but taking personal identity as insignificant in empathically imagining how others feel. Schopenhauer is, however, right that, though these attitudes are spontaneously partial, this can be corrected. His morality is also interesting in raising the question rarely discussed in philosophical ethics of how moral virtue relates to ascetic self-renunciation. Both of these ideals are highly demanding, but the book ends by arguing that this is no objection to their validity.

A moral requirement to be universally benevolent could be very demanding, i.e. it could take great sacrifices of the agent’s welfare to live up to it. It has been argued that this is an objection to its validity, but this is denied in this chapter. Any reasonable morality will comprise norms that are quite demanding, e.g. a norm to let ourselves be tortured to death when this is necessary to prevent a million or billion from suffering the same fate. However, the fact that a moral norm is demanding could mean that you are not blameworthy if you fail to comply with it. This fact could also be a pragmatic reason for you not to try to comply with this norm but with a less demanding norm if your failure to comply will have bad consequences.

This chapter presents five claims that are involved in Schopenhauer’s view that compassion is the basis of morality and whose truth is examined in the book. In this chapter it is argued in particular that if, in opposition to him, positive feelings of pleasure and joy are taken to exist in their own right like negative feelings of pain and suffering, compassion cannot be the only moral motive. It must be supplemented by attitudes like sympathy with positive feelings and benevolence. These attitudes are like compassion in being based on empathy. Other claims of his that are examined in the book are that compassion involves identifying with another, that justice is a form of compassion, and that compassion can be universal.

In On What Matters Derek Parfit adopts Henry Sidgwick’s idea of a duality of practical reason consisting in there being personal reasons to care about our own well-being as well as moral reasons to care about everyone else’s well-being. But this sits ill with his well-known claim in Reasons and Persons that personal identity is not what matters. For this implies that were we to divide into two individuals, we would have the same reasons to care about these individuals as ourselves, though they are distinct from us. It is suggested that this is because we empathize with them in the same way as with ourselves in the future, ‘from the inside’, and that considerations of justice do not apply to them because their wills are too dependent on our wills.

Chemistry - a European journal 26(15), 3411 - 3419 (2020). doi:10.1002/chem.201905479, The activation process of a known Ru‐catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X‐ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert‐butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1‐phenylethanol a fast‐dynamic equilibrium was observed., Published by Wiley-VCH, Weinheim

Herein, we report on the use a biohybrid catalyst consisting of palladium nanoparticles immobilized on cross-linked enzyme aggregates of lipase B of Candida antarctica (CalB CLEA) for the dynamic k ...

We present an analysis of a notion of the meaning of life, according to which our lives have meaning if we spend them intentionally producing what has value for ourselves or others. In this sense our lives can have meaning even if a science-inspired view of the world is correct, and they are only transient phenomena in a vast universe. Our lives are more or less meaningful in this sense due to the difference in value for ourselves and others we intentionally create while leading them. These inequalities are morally unjustifiable because they are ultimately due to factors beyond our responsibility and control. But from the point of view of eternity these differences in meaningfulness and value dwindle to insignificance, and this offers some consolation for the unjustifiable inequalities.

The K-edge X-ray absorption near-edge structure (XANES) spectra of 19 phosphorus-containing compounds have been measured in solution. The energy at maximum intensity of the primary phosphate peak, regardless of chemical species, is 2154.5 ± 0.4 eV. A few of the compounds studied feature XANES spectra which are conceivably characteristic enough to be used as positive identifiers in solution, including O,O-diethyldithiophosphate, (C2H5O)2PS(SH), triphenylphosphine oxide, (C6H5)3PO, and triphenylphosphite (C6H5O)3P. However, most spectra are near-identical or similar enough to another compound to prohibit any useful quantification analysis. The narrow range of absorption edge energy, and all phosphorus compounds studied have an absorption edge at higher energy than elemental phosphorus (red phosphorus). This shows that the electron density of phosphorus in these compounds is lower than in elemental phosphorus, and the conventional use of oxidation numbers cannot be applied.

This chapter discusses the relations between moral status (or standing) and what the author calls moral significance. Something has moral significance just in case it morally counts for its own sake, or is something that must be taken into consideration in itself when moral judgments about what ought or ought not to be done are made. The chapter argues that the moral status of something is dependent on what is morally significant about it. Nothing can have moral status if there is not anything morally significant about it. On the other hand, something can be morally significant, even though it does not have moral status. The notion of moral significance is then the more fundamental notion and the notion of moral status could be dispensed with. In fact, it would simplify and clarify matters if it were dispensed with.

This paper aims to show that between Reasons and Persons and On What Matters the orientation of Derek Parfit’s philosophy underwent a significant change. The approach of Reasons and Persons is largely revisionist, which is exemplified by his reductionist account of personal identity. This account is omitted in On What Matters apparently because it does not fit in with the conciliationist project of this work. The aim of the first two volumes of that work is to show that, on the basis of a non-naturalist theory of normative reasons, three supposedly irreconcilable moral theories—rule-consequentialism, Kantian and Scanlonian contractualism—could converge to form a single Triple Theory. In the third volume, the conciliationist approach is carried further by Parfit’s attempt to show both that his metaethical position is in essential agreement with rivals, such as Gibbard’s expressivism, and to reconcile parts of common-sense morality and consequentialism in order to bring them together in the Triple Theory. This chapter argues that the failure of these attempts as well as the fact that the most controversial revisionist claims in Reasons and Persons are left out throw doubt on the feasibility of Parfit’s conciliationalist undertaking.

X-ray absorption spectroscopy (XAS) has been employed to study the coordination of the Ag

The structures of the solvated copper(II) ion in water and nine organic oxygen donor solvents with similar electron-pair donor ability, but with different space-demanding properties at coordination, have been studied by EXAFS. N,N′-Dimethylpropyleneurea and N,N,N′,N′-tetramethylurea are sufficiently space demanding at coordination to make the axial positions not accessible, resulting in square-planar copper(II) solvate complexes with an intense green color. The mean Cu–O bond distances in these two solvate complexes are 1.939(3) and 1.935(3) Å, respectively. The best fits of the remaining solvates, which are light blue in different hues, are obtained with a Jahn–Teller distorted-octahedral model consisting of four strongly bound solvent molecules in the equatorial positions at 1.96(2) Å and two in the axial positions but with different Cu–Oax bond distances: ca. 2.15 and 2.32 Å. This is in agreement with observations in solid-state structures of compounds containing hexaaquacopper(II) complexes crystallizing in noncentrosymmetric space groups and all reported crystal structures containing a [Cu(H2O)5(O-ligand)] complex with Jahn–Teller distortion. Such a structure is in agreement with previous EPR and EXAFS studies proving the hydrated copper(II) ion to be a noncentrosymmetric complex in aqueous solution. The refinements of the EXAFS data of the solids [Cu(H2O)6](ClO4)2, [Cu(H2O)6](BrO3)2, [Cu(H2O)6]SiF6, Cu(NO3)2·2.5H2O, and CuSO4·5H2O gave Cu–O bond distances significantly different from those reported in the crystallographic studies but similar to the configuration and bond distances in the hydrated copper(II) ion in aqueous solution. This may depend on whether the orientation of the axial positions is random in one or three dimensions, giving a mean structure of the solid with symmetry higher than that of the individual complexes. This study presents the very first experimental data from the new X-ray absorption spectroscopy beamline Balder at the MAX IV synchrotron radiation facility in Lund, Sweden, as well as the utilized properties of the beamline., The coordination chemistry of the solvated copper(II) ion has been studied in 10 solvents, including water. The copper(II) ion has a noncentrosymmetric Jahn−Teller distorted-octahedral geometry with the axial Cu−O bond distances differing by ca. 0.2 Å.

There are no egalitarians in a pandemic. The scale of the challenge for health systems and public policy means that there is an ineluctable need to prioritize the needs of the many. It is impossible to treat all citizens equally, and a failure to carefully consider the consequences of actions could lead to massive preventable loss of life. In a pandemic there is a strong ethical need to consider how to do most good overall. Utilitarianism is an influential moral theory that states that the right action is the action that is expected to produce the greatest good. It offers clear operationalizable principles. In this paper we provide a summary of how utilitarianism could inform two challenging questions that have been important in the early phase of the pandemic: (a) Triage: which patients should receive access to a ventilator if there is overwhelming demand outstripping supply? (b) Lockdown: how should countries decide when to implement stringent social restrictions, balancing preventing deaths from COVID-19 with causing deaths and reductions in well-being from other causes? Our aim is not to argue that utilitarianism is the only relevant ethical theory, or in favour of a purely utilitarian approach. However, clearly considering which options will do the most good overall will help societies identify and consider the necessary cost of other values. Societies may choose either to embrace or not to embrace the utilitarian course, but with a clear understanding of the values involved and the price they are willing to pay.

A very slow oxidation of dimethylsulfoxide (dmso) solvated tin(II) ions in solution results in the formation of a crystalline, structurally determined compound, [CH3Sn(OS(CH3)2)5](ClO4)3, whereas a similar reaction in N,N-dimethylthioformamide (dmtf) forms a crystalline solid with a proposed binuclear [Sn2(SH)2(SCHN(CH3)2)8]6+ entity but whose exact formula remains undetermined. Both solids precipitate with time in their respective mother liquids and constitute the first two tin(IV) and even tetravalent d10 metal ion solvate complexes ever reported. An EXAFS study showed that the structure of the [CH3Sn(OS(CH3)2)5]3+ complex is identical in solid state and dmso solution. While the exact chemical reaction pathways are unknown, the formation of these complexes constitute a novel way of obtaining solvated tin(IV) ions in standard, commonplace organic media.

In situ X-ray absorption spectroscopy (XAS) investigations have been performed to provide insights into the reaction mechanism of a palladium(II) catalyzed undirected C–H acetoxylation reaction in the presence of an oxidant. A Pd(II) N-heterocyclic carbene complex π-stacked onto reduced graphene oxide (rGO) was used as the catalyst. The Pd speciation during the catalytic process was examined by XAS, which revealed a possible mechanism over the course of the reaction. Pd(II) complexes in the as-synthesized catalyst first go through a gradual ligand substitution where chloride ions bound to Pd(II) are replaced by other ligands with a mean bond distance to Pd matching Pd–C/N/O. Parallel to this the mean oxidation state of Pd increases indicating the formation of Pd(IV) species. At a later stage, a fraction of the Pd complexes start to slowly transform into Pd nanoclusters. The mean average oxidation state of Pd decreases to the initial state at the end of the experiment which means that comparable amounts of Pd(0) and Pd(IV) are present. These observations from heterogeneous catalysis are in good agreement with its homogeneous analog and they support a Pd(II)–Pd(IV)–Pd(II) reaction mechanism.

The structures of hydrated phosphoric acid and phosphate ions (H2PO4–, HPO42–, and PO43–) in aqueous solution have been determined by P K-edge EXAFS and large angle X-ray scattering (LAXS). The P–O bond distance in all phosphate species studied is close to 1.53 A. The P–(O)···Oaq distances have been refined to ca. 3.6 A from the LAXS data giving a P–O···Oaq bond angle close to tetrahedral, suggesting that each oxygen or OH group of phosphoric acid and dihydrogen phosphate, on average, hydrogen bind three water molecules. The (P−)O(−H)···Oaq and (P−)O···(H−)Oaq hydrogen bonds in hydrated phosphoric acid and the H2PO4– ion are shorter than the hydrogen bonds in neat water. This supports previous infrared spectroscopic studies claiming that the hydrogen bonds in hydrated phosphoric acid and phosphate ions are stronger than the hydrogen bonds in neat water. Phosphoric acid and phosphate ions can therefore be regarded as structure making solutes. This is the first study applying transmission mode X-ray absorpt...

Amorphous calcium carbonate (ACC), with the highest reported specific surface area of all current forms of calcium carbonate (over 350 m2 g-1), was synthesized using a surfactant-free, one-pot meth ...

A series of concentrated aqueous solutions of ferric chloride with different chloride:iron(III) ratios has been studied by means of EXAFS to determine the structure around the iron(III) ion of the dominating species in such solutions. The dominating species in dilute acidic aqueous solution of ferric chloride, at less than 1 mmol·dm−3, are the hydrated iron(III) and chloride ions, while in concentrated aqueous solution and in solutions with an excess of chloride ions, up to 1.0 mol·dm−3, it is the trans-[FeCl2(H2O)4]+ complex. Possible higher chloroferrate(III) or dimeric [Fe2Cl6] complexes at room temperature, as proposed in the literature, were not observed in any of the studied solutions in spite of an excess of chloride ions of 1 mol·dm−3. Electronic supplementary material The online version of this article (10.1007/s10953-018-0756-6) contains supplementary material, which is available to authorized users.

The structures of the solvated zinc ion and the solvated zinc–iodide complexes in methanol solution have been determined by EXAFS. The zinc ion is six-coordinated in an octahedral fashion with a mean Zn–O bond distance of 2.071(4) Å. According to the stability constants of the zinc–iodide system in methanol solution the first complex, ZnI+, is suppressed, which may indicate that a coordination change takes place at this step. On the other hand, the second complex, ZnI2, predominates at excess of iodide. The methanol solvated ZnI2 complex has a tetrahedral structure with mean Zn–I and Zn–O bond distances of 2.55(1) and 1.99(1) Å, respectively. The mean Zn–I bond distance in a solution containing a maximal content of ZnI+, ca. 12%, strongly indicates that the first complex also has a tetrahedral structure. Electronic supplementary material The online version of this article (10.1007/s10953-018-0737-9) contains supplementary material, which is available to authorized users.

The structures of the monohalomercury(II) complexes, [HgX]+, in dimethylsulfoxide (dmso), pyridine and N,N-dimethylthioformamide (dmtf) solution have been studied by means of EXAFS. All complexes in the Hg2+-X− systems, X = Cl, Br and I, in dmso and pyridine have the unique property with wide range of predominance of all individual complexes. This means that all complexes can be individually characterized in solution. The previously reported complex formation thermodynamics in dmso and pyridine predicted a substantial desolvation at the formation of the first complex. This study shows that the dmso and pyridine solvated [HgX]+ complexes have one solvent molecule strongly bound “trans” to the halide ion and another two weakly bound solvent molecules in the remaining positions of linearly distorted tetrahedra. This shows that a substantial desolvation of the hexasolvated mercury(II) ions takes place at the formation of the [HgX]+ complexes. The strongly bound dmso molecule binds through its oxygen atom to mercury(II) in the [HgCl]+ and [HgBr]+ complexes, while in the [HgI]+ complex through its sulfur atom. The Hg–X bonds are slightly shorter in the [HgX]+ complexes than in corresponding [HgX2] complexes, and the short Hg–O and Hg–N bond distances are ca. 0.35 and 0.25 A shorter than in the octahedral hexakis(dmso)- and -(pyridine)mercury(II) solvates, respectively. In dmtf solution, the dmtf solvated mercury(II) ion is four-coordinate in tetrahedral fashion. The structures of the dmtf solvated [HgX]+ complexes show the same basic tetrahedral configuration as the mercury(II) solvate. This shows that a simple substitution reaction takes place at the formation of the [HgX]+ complexes in dmtf.

This is a reply to Jesse Prinz and Paul Bloom’s skepticism about the moral importance of empathy. It concedes that empathy is spontaneously biased to individuals who are spatio-temporally close, as well as discriminatory in other ways, and incapable of accommodating large numbers of individuals. But it is argued that we could partly correct these shortcomings of empathy by a guidance of reason because empathy for others consists in imagining what they feel, and, importantly, such acts of imagination can be voluntary – and, thus, under the influence of reflection – as well as automatic. Since empathizing with others motivates concern for their welfare, a reflectively justified empathy will lead to a likewise justified altruistic concern. In addition, we argue that such concern supports another central moral attitude, namely a sense of justice or fairness.

Solution chemistry is commonly regarded as the physical chemistry of reactions and chemical equilibria taking place in the bulk of a solvent, and between solutes in solution, and solids or gases in contact with the solution. Our knowledge about such reactions and equilibria in aqueous solution is very detailed such as their physico–chemical constants at varying temperature, pressure, ionic medium and strength. In this paper the solution chemistry in the surface region of aqueous solutions, down to ca. 10 Å below the water–air interface, will be discussed. In this region, the density and relative permittivity are significantly smaller than in the aqueous bulk strongly affecting the chemical behaviour of solutes. Surface sensitive X-ray spectroscopic methods have recently been applicable on liquids and solutions by use of liquid jets. This allows the investigation of the speciation of compounds present in the water–air interface and the surface region, a region hardly studied before. Speciation studies show overwhelmingly that neutral molecules are accumulated in the surface region, while charged species are depleted from it. It has been shown that the equilibria between aqueous bulk, surface region, solids and/or air are very fast allowing effective transport of chemicals over the aqueous surface region.

X-ray absorption spectroscopy (XAS) has been employed to study the coordination of the Ag+ ion in aqueous solution. The conjunction of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) data analysis provided results suggesting the preference for a first shell linear coordination with a mean Ag-O bond distance of 2.34(2) A, different from the first generally accepted tetrahedral model with a longer mean Ag-O bond distance. Ab initio molecular dynamics simulations with the Car-Parrinello approach (CPMD) were also performed and were able to describe the coordination of the hydrated Ag+ ion in aqueous solution in very good agreement with the experimental data. The high sensitivity for the closest environment of the photoabsorber of the EXAFS and XANES techniques, together with the long-range information provided by CPMD and large-angle X-ray scattering (LAXS), allowed us to reconstruct the three-dimensional model of the coordination geometry around the Ag+ ion in aqueous solution. The obtained results from experiments and theoretical simulations provided a complex picture with a certain amount of water molecules with high configurational disorder at distances comprised between the first and second hydration spheres. This evidence may have caused the proliferation of the coordination numbers that have been proposed so far for Ag+ in water. Altogether these data show how the description of the hydration of the Ag+ ion in aqueous solution can be complex, differently from other metal species where hydration structures can be described by clusters with well-defined geometries. This diffuse hydration shell causes the Ag-O bond distance in the linear [Ag(H2O)2]+ ion to be ca. 0.2 A longer than in isolated ions in solid state.

The calcium(II), iron(III) and chromium(III) alkyl-N-iminodiacetate systems have been studied in aqueous solution with respect to stability, acid–base properties and structure. The calcium(II) ion forms only one weak complex with methyl-N-iminodiacetic acid in water, K1 = 12.9 (2) mol–1⋅dm3, while iron(III) and chromium(III) form very stable complexes with alkyl-N-iminodiacetic acids. The calcium(II)–methyl-N-iminodiacetate complex is octahedral in the solid state with most probably water in the remaining positions giving a mean Ca–O bond distance of ca. 2.36 Å. The iron(III) alkyl-N-iminodiacetate complexes have low solubility due to a strong tendency to form polymeric structures. Depending on pH in the solution at their preparation, the degree of hydrolysis in the resulting compound(s) may differ. In the solid state, the polymeric iron(III) alkyl-N-iminodiacetate compounds seem to have the mean composition Fe2O(Cx-IDA)5; the mean Fe–O bond distances to the oxo group and the alkyl-N-iminodiacetate ligands are 1.92 and 2.02 Å, respectively. In these complexes the nitrogen atoms are bound at much longer bond distances, 0.1–0.2 Å, than the carboxylate oxygens. This distribution with short strong Fe–O bonds and much longer and weaker Fe–N bonds is also found in most other structurally characterized iron(III) carboxylated amine/polyamine complexes. The chromium(III) alkyl-N-iminodiacetate complexes are octahedral in both solution and solid state, and the low solubility of the solid compounds indicates a polymeric structure with the ligands bridging chromium(III) ions. Also, chromium(III) binds oxygen atoms in carboxylated amines at significantly shorter distance than the nitrogen stoms. The chromium(III) alkyl-N-iminodiacetate complexes display such slow kinetics at titration with strong base that the back-titration with strong acid shows completely different acid–base properties, thus the acid–base reactions are irreversible.

Amorphous calcium phosphate (ACP) has shown significant effects on the biomineralization and promising applications in bio-medicine. However, the limited stability and porosity of ACP material restrict its practical applications. A storage stable highly porous ACP with Brunauer–Emmett–Teller surface area of over 400 m2/g was synthesized by introducing phosphoric acid to a methanol suspension containing amorphous calcium carbonate nanoparticles. Electron microscopy revealed that the porous ACP was constructed with aggregated ACP nanoparticles with dimensions of several nanometers. Large angle X-ray scattering revealed a short-range atomic order of

According to the definition proposed by this chapter you intentionally perform the basic bodily action of causing p now if you now have an occurrent decisive desire to cause p directly—that is, without causing anything as a means to it—and this desire now causes something because you correctly and justifiably think that it is p. Since it has been claimed that conscious occurrences are not causally related, this account has to be modified to suit mental acts such as visualizing something. In this connection some rival theories of intentional action which refer to acts of will or volitions are critically examined. Finally, building on the definition of an intentional basic action, the notion of an intentional non-basic action is defined.

You let it be the case that q by refraining from causing p just in case: (a) you correctly believe that if you cause p, q will not be the case, (b) you correctly believe that you have an all-in dual power concerning causing p, (c) you do not decisively desire to cause p because you do not find sufficient reasons for forming such a desire, and (d) q becomes the case because you do not cause p due to (c). Since refraining is intentional, it importantly follows from this that characterizing something as intentional does not involve causality. Moreover, when we can refrain from causing something, we must have the all-in dual power of causing it and avoiding to do so. Thus, the concept of refraining raises questions about free will and responsibility which are briefly discussed.

An advantage of using conditionals as the standard formula for reasons for action is that the conditional form can also be used to bring out the structure of reasons for belief—thus making possible a close comparison between these kinds of reasons and reasoning. It then becomes apparent that the direction of derivation is the reverse in the practical case when we reason our way to desiring sufficient means to an end from desiring the end to the theoretical case when we derive beliefs from sufficient conditions for their truth. This reversal reflects the opposite direction of fit of beliefs and desires. The implications of this account of reasoning with desires for the moral doctrine of the double effect and for reasoning with respect to emotions are briefly considered.

It is here argued that when we act for a reason, the consequent of this reason(-conditional) must specify something that we desire. Intelligent desires, which are involved in intentional action, are distinguished from non-intelligent desires. It is intelligent desires which are ‘decisive’ that determine our intentional actions. Such desires can be said to be formed by decisions, but not necessarily decisions preceded by deliberation. You have an occurrent decisive desire to cause p now just in case you are in an internal state which, along with its underlying thought that you can now cause p (and thereby cause consequences specified by reasons that you may have for causing p), causes something to become a fact because you think that it is that p (and thereby will have the specified consequences).

The overarching aim of this book is to provide a reductionist analysis of what it is to act for a reason in such a way that we intentionally perform the action that we have a reason for performing—an action that will in the end be a basic action—and intentionally achieve the end or goal for which we do this action, as specified by the reason. This analysis of intentional action is reductionist in the sense that it does not appeal to any irreducibly action-theoretical concepts. It does not refer to anything that is unanalysably an action in virtue of involving either a unique type of agent-causation, or anything like a volition, trying, or decision that is assumed to be an act(ion) in a primitive sense. Nor does it refer to any unanalysable states or attitudes that are essentially directed at actions, like intentions and desires (to act). It does refer to a kind of desire—decisive desire—but it is in turn analysed as the causal power of some physical states in conjunction with propositional thinking. The direction of fit between thought and fact here is not that something is thought to fit the facts, but that something is caused to be fact because of how it is thought of....