Effects of solvent structure on electron reactivity and radiolysis yields: 2-propanol/water mixed solvents

1984 ◽  
Vol 62 (7) ◽  
pp. 1265-1270 ◽  
Author(s):  
Joanna Cygler ◽  
Gordon R. Freeman
Keyword(s):  
Pure Water ◽  
Mixed Solvents ◽  
Water Structure ◽  
Trap Depth ◽  
Solvent Structure ◽  
Solvated Electrons ◽  
Absorption Energy ◽  
Diffusion Controlled ◽  
Free Ion ◽  
Different Temperatures

Reaction of solvated electrons with nitrobenzene, N, is nearly diffusion controlled in both pure solvents; kN ~ 1010 dm3/mol s. The value of kN is approximately proportional to the inverse viscosity η−1 in the pure solvents, and in the mixed solvents at different temperatures. However, on going from zero to 74 mol% water at the same temperature kN is independent of the 40% increase of η. Electron diffusion in the mixed solvents is not a simple function of fluidity.Reaction with the inefficient scavengers tryptophane (kS ~ 109 dm3/mol s) and phenol (kS ~ 107–108 dm3/mol s) correlates inversely with the electron optical absorption energy. The latter is related to the trap depth in the solvent; electrons in deeper traps have less tendency to react with molecules of low electron affinity.Addition of 3 mol% 2-PrOH to water at 296 K increases the value of Gεmax by 16%, although the value in pure 2-PrOH is three-fold smaller than that in pure water. The increase is attributed to an increase in the free ion yield, caused by an increase in the product of the electron thermalization range and the microscopic dielectric constant of the fluid between the ion and electron, averaged over the time that they exist as a correlated pair. Addition of a small amount of alcohol to water increases the orderliness of the water structure.

Solvent structure effects on electron thermalization ranges in water–alcohol mixed solvents; preferred EAmax values for e−s in alcohols

1983 ◽  
Vol 61 (6) ◽  
pp. 1115-1119 ◽  
Author(s):  
Ah-Dong Leu ◽  
Kamal N. Jha ◽  
Gordon R. Freeman
Keyword(s):  
Energy Loss ◽  
Mixed Solvents ◽  
Solvent Structure ◽  
Solvated Electrons ◽  
Pure Solvent ◽  
Free Ion ◽  
Rotational Motions ◽  
Stiffening Effect ◽  
Water Alcohol

Addition of 2 mol% of an alcohol to water or of 1 mol% of water to an alcohol increases the value of Gfi εmax (e−s) above that in the pure solvent. The effect is attributed mainly to an increasing free ion yield Gfi. The increase of Gfi correlates with a "stiffening" of the solvent molecular rotational motions and a corresponding lower rate of energy loss by the epithermal electrons to dipole rotations. Thus the increase of Gfi is mainly attributed to a larger electron thermalization range bGP. The value of Gfi εmax passes through a maximum at 2 mol% of an alcohol in water; the maximum increases in the order methanol< ethanol< 1-propanol as additive. The solvent "stiffening" effect of these solutes increases in the same order.Some of the published values of EAmax and W1/2 for solvated electrons in alcohols appear to be too low. A set of preferred values is reported herein.

scholarly journals Optical absorption spectra of solvated electrons in 1-butylamine–water mixed solvents

1995 ◽  
Vol 73 (12) ◽  
pp. 2126-2130 ◽  
Author(s):  
Yixing Zhao ◽  
Gordon R. Freeman
Keyword(s):  
Optical Absorption ◽  
Absorption Spectra ◽  
Pure Water ◽  
Mixed Solvents ◽  
Binary Solvents ◽  
Optical Absorption Spectra ◽  
Solvated Electron ◽  
Solvated Electrons ◽  
Selective Solvation ◽  
Ideal Mixing

The optical absorption spectra of es− in 1-butylamine–water mixed solvents increase smoothly in energy and intensity as the water content is increased, with the exception of a small decrease in intensity on going from 95 to 100 mol% water. At 298 K the value of Gεmax increases from 1.42 × 10−21 m2/16 aJ (8.6 × 103 es−L/100 eV mol cm) in pure 1-butylamine to 8.3 × 10−21 m2/16 aJ (50 × 103 es−L/100 eV mol cm) in pure water, and the value of EAmax increases from 115 zJ (0.72 eV) to 278 zJ (1.74 eV). In the pure amine, if G(es−) = 0.27, then εmax = 5.3 × 10−21 m2/es− (3200 m2/mol). The solvent composition dependences of Gεmax and EAmax indicate little selective solvation of es− by water; this might be due to relatively "ideal" mixing of water and amine in the binary solvents. The temperature coefficient −dEAmax/dT = 0.43 zJ/K in pure 1-butylamine, 0.47 in pure water, and has a minimum of 0.27 in the 50:50 mixture. Keywords: 1-butylamine–water mixed solvents, optical absorption spectra, solvated electron, temperature dependence.

Article

1998 ◽  
Vol 76 (4) ◽  
pp. 407-410
Author(s):  
Yixing Zhao ◽  
Gordon R Freeman
Keyword(s):  
Pure Water ◽  
Mixed Solvents ◽  
Molar Conductivity ◽  
Solvated Electron ◽  
Pure Ethanol ◽  
Electrical Conductances ◽  
Alcohol Water ◽  
Different Temperatures ◽  
Ion Radius ◽  
Pure Methanol

As a foundation for a future measurement of solvated electron mobilities in alcohol-water mixed solvents, the electrical conductances of sodium tetraphenylboride (STPB) in methanol-water, ethanol-water, and 2-propanol-water were measured at different temperatures. The molar conductivity LAMBDA 0 (10-4 S m2 mol-1) of STPB at 298 K is 70 in pure water and 82 in pure methanol; in methanol-water mixed solvents it passes through a minimum, the value being 45 at 70 mol% water. In 2-propanol-water LAMBDA 0 (10-4 S m2 mol-1) at 298 K decreases rapidly from 70 in pure water to 22.6 in 80 mol% water, then gradually to 16.5 in pure 2-propanol. Behavior in ethanol-water is intermediate, with a minimum of 29.5 in 70 mol% water, gradually increasing to 35.5 in pure ethanol. The product of LAMBDA 0 and the solvent viscosity eta has a maximum at about 75 mol% water in methanol, 90 mol% water in ethanol, and 95 mol% water in 2-propanol. The effects are attributed to changes of solvent structure and of solvated ion radius as alcohol is added to water.Key words: alcohol-water mixed solvents, electrical conductivity, large ions, solvent effects, activation energy.

Solvent effects on the reactivity of solvated electrons with ions in isobutanol/water mixed solvents

1994 ◽  
Vol 72 (4) ◽  
pp. 1083-1093 ◽  
Author(s):  
Ruzhong Chen ◽  
Yuris Avotinsh ◽  
Gordon R. Freeman
Keyword(s):  
Proton Transfer ◽  
Pure Water ◽  
Mixed Solvents ◽  
Transition Metal Ions ◽  
Dielectric Relaxation Time ◽  
Solvated Electrons ◽  
Neutral Species ◽  
Water Solvent ◽  
Solvation Structure ◽  
Hydrogen Bonded

The effective reaction radii KRr, where Rr is the reactive encounter radius and K is the probability of reaction per encounter, for [Formula: see text] with [Formula: see text], are all 0.7 ± 0.1 nm in isobutanol containing 10–20 mol% water. The value remains at 0.7 ± 0.1 nm for [Formula: see text] in pure isobutanol, and for the two transition metal ions in pure water solvent. The value for [Formula: see text] reduces to 0.35 nm in pure isobutanol and pure water solvents, whereas for [Formula: see text] in pure water solvent it is only 0.14 nm and 2.6 × 10−5 nm, respectively. The low reactivity of [Formula: see text] with [Formula: see text] in water is attributed to the symmetry of the hydrogen-bonded solvation structure of [Formula: see text] in water, and the higher reactivity of [Formula: see text] is attributed to the lower symmetry of its hydrogen-bonded solvation structure. The [Formula: see text] ions have no low-lying orbital for an electron to occupy, so either reaction occurs by proton transfer to the electron site or the neutral species must decompose. We suggest that the proton transfer or the decomposition of the neutral species is facilitated by an unsymmetrical solvation structure.Reaction of [Formula: see text] in Al(ClO4)3 solutions in water is due mainly to [Formula: see text] from hydrolysis of [Formula: see text] and partly to partially hydroxylated aluminum(III) species. Reaction of [Formula: see text] with [Formula: see text] itself appears to be negligible in water. The reactivity of the solutions of Al(ClO4)3 in isobutanol-rich solvents is 3–5 times greater than that in water.In pure C1 to C4 1-alcanol solvents the value of [Formula: see text] increases linearly with the dielectric relaxation time τ1 of the solvent. In these solvents the probability of permanent capture per encounter increases approximately as the square of the encounter duration.

Electron behavior in mixed solvents: optical spectra and reactivities in water/alkane diols

1984 ◽  
Vol 62 (11) ◽  
pp. 2217-2222 ◽  
Author(s):  
K. M. Idriss-Ali ◽  
Gordon R. Freeman
Keyword(s):  
Optical Absorption ◽  
Reaction Rate ◽  
Composition Range ◽  
Mixed Solvents ◽  
Solvated Electrons ◽  
Reaction Rate Constants ◽  
Diffusion Controlled ◽  
Entropy Of Activation ◽  
Lower Entropy ◽  
The Difference

Investigation of the effect of solvent structure on the optical absorption spectrum and reactivity of solvated electrons has been extended to diol/water mixed solvents, using 1,2-ethanediol (12ED) and 1,4-butanediol (14BD). The large effects that had been found in mono-ol/water mixed solvents did not occur in diol/water. Although addition of 3 mol% of a diol to water increased the optical absorption energies of e−s by 0.06 eV, similar to the shift caused by addition of 3 mol% of a mono-ol, the variation of the spectrum over the rest of the composition range was nearly ideal in diol/water, in contrast to the very non-ideal variation in mono-ol/water. Reaction rate constants kS at 298 K in the diol/water mixed solvents vary approximately as the inverse viscosity,η−1.0, in the diffusion-controlled limit. However, when reactions are two or three orders of magnitude slower than diffusion controlled, kS at 298 K is independent of η. Toluene reacts with e−s at a 10−3-fold smaller rate than does nitrobenzene; the difference is nearly completely due to a ~50 J/mol K lower entropy of activation of the former reaction.

Solvent Structure Effects and Diffusion Control in the Reaction Between Solvated Electrons and Solvated Protons in Alcohols and Water

1972 ◽  
Vol 50 (18) ◽  
pp. 3073-3075 ◽  
Author(s):  
K. N. Jha ◽  
G. L. Bolton ◽  
G. R. Freeman
Keyword(s):  
Reaction Rates ◽  
Diffusion Control ◽  
Solvent Structure ◽  
Solvated Electrons ◽  
Solvent Dependence ◽  
Diffusion Controlled ◽  
Water Effects ◽  
And Diffusion ◽  
Debye Equation

The rates of reactions 1 and 2 are diffusion controlled in alcohols[Formula: see text]In water reaction 1 is slower and reaction 2 (where RO− is HO−) is faster than one would estimate from the Debye equation for diffusion controlled reactions. The solvent dependence of the relative values of k1 and k2 is attributed to the solvent dependence of the structures of [Formula: see text] [Formula: see text] [Formula: see text] and H+ and RO− are strong solvent structure makers in alcohols and in water, whereas e− is a weak solvent structure maker in alcohols and a strong structure breaker in water. Effects of the solvent structure making and breaking properties of ions on their reaction rates have been proposed by Gurney and Frank.

Effect of organic compounds on electrolyte chemical potential in aqueous solutions at various temperatures

1981 ◽  
Vol 59 (13) ◽  
pp. 1872-1877
Author(s):  
David M. Mohilner ◽  
Takashi Kakiuchi ◽  
Joanna Taraszewska
Keyword(s):  
Aqueous Solutions ◽  
Chemical Potential ◽  
Pure Water ◽  
Water Structure ◽  
Lead Sulfate ◽  
Glass Electrode ◽  
Liquid Junction ◽  
Emf Measurements ◽  
Different Temperatures ◽  
Lead Amalgam

Data are reported on the concentration of Na2SO4 required to hold its chemical potential equal to its value in a 0.10045 m solution in pure water for aqueous solutions containing 2-butanol and 1-propanol at six different temperatures. The data were obtained from emf measurements on a galvanic cell without liquid junction containing a sodium reversible glass electrode and a 2-phase lead amalgam – lead sulfate electrode. The results of the measurements are interpreted in terms of the water structure making properties of the organic compound.

Effect of solvent structure on electron reactivity: 2-propanol/water mixtures

1988 ◽  
Vol 66 (7) ◽  
pp. 1706-1711 ◽  
Author(s):  
Yadollah Maham ◽  
Gordon R. Freeman
Keyword(s):  
Electron Transfer ◽  
Secondary Alcohol ◽  
Mixed Solvents ◽  
Trap Depth ◽  
Large Change ◽  
Solvent Composition ◽  
Solvated Electrons ◽  
Tertiary Alcohols ◽  
Alcohol Water ◽  
Small Change

The reactivity of solvated electrons [Formula: see text] with efficient (nitrobenzene, acetone) and inefficient (phenol, toluene) scavengers is affected greatly by the solvent composition in 2-propanol/water mixed solvents. 2-Propanol is the only secondary alcohol that is completely miscible with water. The variation of the nitrobenzene rate constant k2 with solvent composition displays four viscosity zones, as in primary and tertiary alcohol/water mixtures. In zone (c), where the Stokes–Smoluchowski equation applies, the nitrobenzene k2 values in the secondary alcohol/water mixtures are situated between those in the primary and tertiary alcohols, due to the relative values of the dielectric permittivity ε. The charge–dipole attraction energy varies as ε−1.The two water-rich zones (c) and (d) are characterized by a large change of viscosity η and a small change in [Formula: see text] solvation energy (trap depth) Er; here k2 for all the scavengers correlates with the inverse of the viscosity. In the two alcohol-rich zones (a) and (b) the change of η is small but that of Er is large; here k2 of inefficient scavengers correlates with the inverse of Er, due to the difficulty of electron transfer out of deeper traps. Activation energies E2 and entropies [Formula: see text] also show composition zone behaviour. The value of [Formula: see text] is more negative for less efficient scavengers; E2 varies less and does not correlate with reactivity or Er. Electron transfer from solvent to inefficient scavenger is driven by solvent rearrangement around the reaction center, reflected in [Formula: see text].

scholarly journals Behavior and properties of water in silicate melts under deep mantle conditions

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Bijaya B. Karki ◽  
Dipta B. Ghosh ◽  
Shun-ichiro Karato
Keyword(s):  
Electrical Conductivity ◽  
Molar Volume ◽  
Water Solution ◽  
Pure Water ◽  
Electrical Conductance ◽  
Water Structure ◽  
Bulk Water ◽  
Silicate Melts ◽  
Pressure Regime ◽  
Low Pressures

AbstractWater (H2O) as one of the most abundant fluids present in Earth plays crucial role in the generation and transport of magmas in the interior. Though hydrous silicate melts have been studied extensively, the experimental data are confined to relatively low pressures and the computational results are still rare. Moreover, these studies imply large differences in the way water influences the physical properties of silicate magmas, such as density and electrical conductivity. Here, we investigate the equation of state, speciation, and transport properties of water dissolved in Mg1−xFexSiO3 and Mg2(1−x)Fe2xSiO4 melts (for x = 0 and 0.25) as well as in its bulk (pure) fluid state over the entire mantle pressure regime at 2000–4000 K using first-principles molecular dynamics. The simulation results allow us to constrain the partial molar volume of the water component in melts along with the molar volume of pure water. The predicted volume of silicate melt + water solution is negative at low pressures and becomes almost zero above 15 GPa. Consequently, the hydrous component tends to lower the melt density to similar extent over much of the mantle pressure regime irrespective of composition. Our results also show that hydrogen diffuses fast in silicate melts and enhances the melt electrical conductivity in a way that differs from electrical conduction in the bulk water. The speciation of the water component varies considerably from the bulk water structure as well. Water is dissolved in melts mostly as hydroxyls at low pressure and as –O–H–O–, –O–H–O–H– and other extended species with increasing pressure. On the other hand, the pure water behaves as a molecular fluid below 15 GPa, gradually becoming a dissociated fluid with further compression. On the basis of modeled density and conductivity results, we suggest that partial melts containing a few percent of water may be gravitationally trapped both above and below the upper mantle-transition region. Moreover, such hydrous melts can give rise to detectable electrical conductance by means of electromagnetic sounding observations.

scholarly journals Thermodynamic Study of the Solubility of Naproxen in Some 2-Propanol + Water Mixtures

2016 ◽  
Vol 12 (1) ◽  
pp. 48-55 ◽  
Author(s):  
Diego Iván Caviedes Rubio ◽  
Gerson Andrés Rodríguez Rodríguez ◽  
Daniel Ricardo Delgado
Keyword(s):  
Gibbs Energy ◽  
Volume Fraction ◽  
Pure Water ◽  
Water Structure ◽  
Negative Slope ◽  
Driving Mechanism ◽  
Linear Plot ◽  
Enthalpy And Entropy ◽  
The Mean ◽  
Rich Mixtures

The equilibrium solubilities of the anti-inflammatory drug naproxen (NPX) in 2-propanol + water mixtures were determined at several temperatures from 298.15 to 313.15 K. The Gibbs energy, enthalpy, and entropy of solution and of mixing were obtained from these solubility data. The solubility was maximal in φ1 = 0.90 and very low in pure water at all the temperatures studied. A non-linear plot of ∆solnH° vs. ∆solnG° with negative slope from pure water up to 0.20 in volume fraction of 2-propanol and positive beyond this composition up pure 2-propanol was obtained at the mean temperature, 305.55 K. Accordingly, the driving mechanism for NPX solubility in the water-rich mixtures was the entropy, probably due to water-structure loss around non-polar moieties of the drug and for the 2-propanol-rich mixtures it was the enthalpy, probably due to its better solvation of the drug.

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