Yield of solvated electrons in pulse radiolysis of liquid ammonia

Farhataziz,; Perkey, Lewis M.; Hentz, Robert R.

doi:10.1063/1.1681104

Cited by 17 publications

(11 citation statements)

References 16 publications

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“…Combining 34.7, the value of S°(Bg)trM calculated from translational partition function, with 4.1 for S6(Bam"")emp, Sei°= -31 is calculated, which on subsequent combination with S°(Bam) = 79 gives S°(Bam-) = 48. Substitution of 48 for S°(Bam~) in eq 6 gives S°(eam~) = 13, which compares well with 18, a value of S°(eam~) obtained (for conditions in present investigations) from the calculated entropy of eam" by Lepoutre and Jortner. 30 To a good first approximation, the heat of solution of a gaseous ion in a dielectric liquid can be calculated with the Born equation.31 For a 3.7-Á radius of B~2 9 and 16.9 for the dielectric constant of liquid ammonia,98 such calculations give -46 for heat of solution of Bg~i n liquid ammonia.…”

Section: Discussionsupporting

confidence: 86%

“…The values of AHt°a nd AST°o n combination with values of Afff°(Bam) and S°(Bam) respectively give AHf°(Bam-) -AHf°(eam-) = 13 (5) S°(Bam-)-S°(eam-) = 35 (6) Thus a knowledge of the values of AHf°(Bam-) and S°(Bam-) will give values of AHf°(eam-) and S°(eam-)•…”

Section: Discussionmentioning

confidence: 99%

“…The purification of ammonia, and the vacuum line are described elsewhere. [6][7] The vessel used for the determination of solubility of B in liquid ammonia is shown in Figure 1. The volume of the vessel up to any point between marks a and ß is the sum of the previously determined volume up to the mark a and the computed volume of the length of precision bore capil-lary tube between mark a and the point of interest.…”

Section: Methodsmentioning

confidence: 99%

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Pulse radiolytical investigation of the reversible reaction of biphenyl with the solvated electron in liquid ammonia

Farhataziz¹,

Perkey²

1976

J. Phys. Chem.

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From the measured solubility of biphenyl in liquid ammonia for the temperature range 21 to -15.5°, 9.4 kcal mol-1 for the heat of solution and 30 cal deg-1 mol-1 for the entropy of solution for a 1 M standard state are calculated. Nanosecond pulse radiolysis of biphenyl solutions in liquid ammonia show that the reaction of eam~w ith biphenyl produces the biphenyl anion and it is reversible. From the values of the equilibrium constant (the equilibrium concentration of the biphenyl anion divided by the initial concentration of biphenyl and the equilibrium concentration of eam"~) at 21.6 and 10.5°, -20 kcal mol-1 for the heat of reaction and -44 cal deg-1 mol""1 for the entropy of reaction for a 1 M standard state are calculated. The specific rate of the reaction of eam~w ith biphenyl is equal to 1.24 X 10(12"1600/2•3 > for the temperature range 21.6 to -75°. The extinction coefficient of the biphenyl anion at 0.403 µ, the wavelength of maximum absorption, is 3.1 X 104 M-1 cm"1 for the temperature range 23 to -76.5°. The calculated values of the standard heat of formation of eam-and the entropy of eam" for a 1 M standard state are -14 kcal mol-1 and 13 cal deg-1 mol""1, respectively.

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Section: Discussionsupporting

confidence: 86%

Section: Discussionmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Pulse radiolytical investigation of the reversible reaction of biphenyl with the solvated electron in liquid ammonia

Farhataziz¹,

Perkey²

1976

J. Phys. Chem.

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“…d From ref 11 trapolation of the data of Cragoe and Harper.18® For the temperature range from 23 to -75°, a primary yield and average deviation of g(eam") = 3.1 ± 0.3 was calculated from the average values of D at 1.35, 1.45, and 1.75 µ at each temperature and g(eam_) = 3.2 at 23°. 3 At no temperature studied does the decay of eam--(initial concentration ~1.3 µ ) approximate first order. However, a plot of the reciprocal of optical density vs. time becomes increasingly linear with increase in temperature.…”

Section: Resultsmentioning

confidence: 99%

Absorption spectrum, yield, and decay kinetics of the solvated electron in pulse radiolysis of liquid ammonia at various temperatures

Farhataziz¹,

Perkey²

1975

J. Phys. Chem.

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The transient absorption spectrum of eam" induced in neat liquid ammonia by nanosecond pulse radiolysis shifts to higher energies as temperature decreases. The transition energy at the absorption maximum increases from 0.67 to 0.88 eV as temperature decreases from 23 to -75°. The portion of bandwidth at halfmaximum measured from the absorption maximum to the high-energy side of the spectrum is constant over the temperature range from 23 to -75°. For the same temperature range, the primary yield of eam-is constant with a value and average deviation of 3.1 ± 0.3. The mechanism of decay of eam~i n pulse radiolysis of neat liquid ammonia is complex.

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“…Since lower solute concentrations are required in amines our results suggest that the time scale for spur processes must be longer than those observed in water. In liquid ammonia Farhataziz et al (28), comment that Ges-is exceptionally large and, compared to water, indicates some difference in the nature of the spur processes. Further theoretical studies are required to explain this apparent anomaly.…”

Section: Comparisons Wjith Precious Workmentioning

confidence: 99%

Pulse Radiolysis of Liquid Methylamine, Ethylamine, and Ammonia: The Yield of Solvated Electrons

Seddon¹,

Fletcher²,

Sopchyshyn³

et al. 1974

Can. J. Chem.

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. Can. J . Chem. 52.3269 (1974). Yields of solvated electrons, G,,-, have been m e a s~~r e d in both the pure and basic solvents using biphenyl and pyrene as electron scavengers. In pure methylamine and ethylamine G,?-= 2.2 i: 0.1 and 1.8, 1 0.1, respectively. However in basic solution these yields more thar, double giving G,,-= 4.75 f 0.2, Inliquid N H , a n d N D , a t -15"C,GcS-= 3.1, 1 0 . 1 5 a n d 3 . 6 i-0.2, respectively. The latter yields seem independent of base and temperature from -15 to -50 C . Comparisons with previous work are discussed. [Trad~rit par le journal]

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Yield of solvated electrons in pulse radiolysis of liquid ammonia

Cited by 17 publications

References 16 publications

Pulse radiolytical investigation of the reversible reaction of biphenyl with the solvated electron in liquid ammonia

Pulse radiolytical investigation of the reversible reaction of biphenyl with the solvated electron in liquid ammonia

Absorption spectrum, yield, and decay kinetics of the solvated electron in pulse radiolysis of liquid ammonia at various temperatures

Pulse Radiolysis of Liquid Methylamine, Ethylamine, and Ammonia: The Yield of Solvated Electrons

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