Hydration of CN−, NO2−, NO3−, and OH− in the Gas Phase

Payzant, J. D.; Yamdagni, R.; Kebarle, P.

doi:10.1139/v71-551

Cited by 137 publications

(62 citation statements)

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“…Assuming that the theoretical HF and experimental HX results are reliable, the above difference may be rationalized by the stronger covalent contribution to the bonding in F-(HF)?. (c) Lattice energies of M t .X2H-As mentioned in the Introduction, lattice energies of M t X,H-and the binding energies X--HX can be related by means of a Born type cycle (see [12]) where AHL stands for lattice energy. AHL(MX) can be evaluated from experimental data and AH, can be obtained from the experimentally available heats of formation of the reactants.…”

Section: Discussion Of Results ( a ) The Dissociatioti Energies In (Xmentioning

confidence: 99%

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The hydrogen bond energies of the bihalide ions XHX⁻ and YHX⁻

Caldwell¹,

Kebarle²

1985

Can. J. Chem.

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This paper is dedicated to Professor Camille Sandor-or1 the occc~sion of his 65th birtlzdayG. CALDWELL and P. KEBARLE. Can. J. Chem. 63, 1399Chem. 63, (1985.Experimental measurements of the gas phase ion equilibria X + HX = XHX-, X-(HX),,, + HX = X-(HX),,, and X-+ HY = XHY where X, Y = C1, Br. I, with a high pressure mass spectrometer, combined with the recent determination of F-+ HF = FHF-by Larson and McMahon, provide a very complete set of hydrogen bond dissociation enthalpies and free energies for the hydrogen bihalide ions. The bond energy trends In the different XHX-and X H Y are discussed. The data can be used also for the evaluation of lattice energies of salts containing the bihalide ions and for determinations of the solvation energies of these ions. [Traduit par le journal]

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Section: Discussion Of Results ( a ) The Dissociatioti Energies In (Xmentioning

confidence: 99%

“…(11 -I, n) measurements were made has been described previously (8,12). Briefly, a 2000 eV electron beam was pulsed "on" for 10-50 ks and The bond energy, D(Cl--HCl) = 23.7 k~a l /~~l , determined "off" for 2-4 ms through the high pressure ion source.…”

Section: Methodsmentioning

confidence: 99%

The hydrogen bond energies of the bihalide ions XHX⁻ and YHX⁻

Caldwell¹,

Kebarle²

1985

Can. J. Chem.

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“…38 Several existing chloride models 28,39 are, unfortunately, based on this measurement, even though it is generally recognized to be erroneous. 36,40,41 Using these three adjustable parameters to reproduce only two physical properties results in a manifold of potential parameter sets. Figure 1 shows the set of ( ,σ) values that produce the bond lengths and energies required above, for a value of ) 2.307 Å -1 .…”

Section: Polarizable Chloride Ion Modelmentioning

confidence: 99%

Effects of Polarizability on the Hydration of the Chloride Ion

1996

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Polarizable and nonpolarizable potential models for both water and chloride are used to address the issue of surface Vs interior solvation of the chloride ion in Cl(H 2 O) n -clusters, for n up to 255. We find that, even for the largest clusters, simulations with polarizable water models show that the chloride ion is preferentially solvated near the surface of the cluster. This behavior is not observed with a nonpolarizable model. The many-body effects are not directly responsible for this solvation behavior; polarizability appears to be important primarily for its role in facilitating a larger average dipole moment on the water model. Polarizability on the chloride ion is not found to have a substantial effect on the structure of the clusters.

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“…The mole ratios in brackets are equal to the cor-2 2 responding ratios of partial pressures which are used for the gas phase equilibria. Thus, we can substitute from equations (1), (4), and (5) and obtain (6) (7) In presenting the results it is desirable first to seek a most meaningful comparison between the values from these calculations with those from conventiona1 experiments which are mostly for liquid-like conditions. The best conditions for comparison will be at the highest temperature and lowest density of accurate measurement.…”

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Self-ionization of water at high temperature and the thermodynamic properties of the ions

Pitzer¹

1982

J. Phys. Chem.

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+ It is shown that gas phase data on hydrated Hand OH ions from mass spectrometry can be used to calculate the ionization product for water at high temperature "and at high enough pressure to allow relating these results In this paper the properties of gaseous, water-related ions 3 are used to calculate the ion product for steam. These results appear to be valid at pressures gradually increasing with temperature until the curve can be connected with the directly measured experimental values of Quist 4 at 1073 K .-3 and 0.5 g cm • At lower temperatures one can interpolate between these newly calculated curves at lower density and the equation of Marshall and Franck for the high density region. These interpolated curves, although still somewhat uncertain, should be much more reliable than extrapolations considering only the high-density data. and OH should be almost exactly the same as that for NH3 and HF which can be found, as -(Go-HO/RT), in appropriate tab1es. 9 Thus one has the equilibrium constant K1 for reaction (1).But with increasing pressure of H 2 0 most of these ions are further hydrated K n with equilibrium constants K+ and K. Table 1 gives the values of 8Ho and n n n 88° which are derived from these measured equilibria. Also listed are the n * approximate temperatures T where the equilibria were measured.For our purpose we need the sum of the partial pressures of all hydrates of H+ and the corresponding sum for OHWe writewhere the reasons for these definitions will be apparent later. While, at low pressure only the first few hydrates are significant, under higher pressures 3 most of the ions are highly hydrated. Thus a model is needed for hydration equilibria of indefinite order. The expressions labeled A in Table 1 for n ~ 4 represent quite accurately the measured values for n from 4 through 6 5 3,6-7 for positive ions and through 5 for negative ions.Eventually the rate of reduction of -~H for successive values of n will undoubtedly decrease n -1well below the increment of 1 kcal mol given for expression A. Hence, asan al·ternate model B, this quantity is decreased to 0.8 kcal mol • For anygivenT and P, if models Aand'B give the same result, it should be reliable;if they differ slightly, the result for A should be preferred and reliable; while if they differ somewhat more, the correct result should lie between those for A and B. With increasing difference, i.e., very high order of hydration', the correct result may lie on either side of that for model B which should be better than A. Eventually as P increases, this treatment based on gas phase equilibria will become unsatisfactory and this is indicated by a gross difference between the'results from models A and B as well as by substantial departures of the properties of the steam from the ideal gas equation.Also to be considered is the value of ~c for the successive hydration p equilibria. This quantity was neglected in evaluating the mass spectrometric data over a limited range of temperature for a given n. But we will be extrapolating valu...

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Hydration of CN⁻, NO₂⁻, NO₃⁻, and OH⁻ in the Gas Phase

Cited by 137 publications

References 3 publications

The hydrogen bond energies of the bihalide ions XHX⁻ and YHX⁻

The hydrogen bond energies of the bihalide ions XHX⁻ and YHX⁻

Effects of Polarizability on the Hydration of the Chloride Ion

Self-ionization of water at high temperature and the thermodynamic properties of the ions

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Hydration of CN−, NO2−, NO3−, and OH− in the Gas Phase

Cited by 137 publications

References 3 publications

The hydrogen bond energies of the bihalide ions XHX− and YHX−

The hydrogen bond energies of the bihalide ions XHX− and YHX−

Effects of Polarizability on the Hydration of the Chloride Ion

Self-ionization of water at high temperature and the thermodynamic properties of the ions

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Product

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Hydration of CN⁻, NO₂⁻, NO₃⁻, and OH⁻ in the Gas Phase

The hydrogen bond energies of the bihalide ions XHX⁻ and YHX⁻

The hydrogen bond energies of the bihalide ions XHX⁻ and YHX⁻