Pulse radiolysis of aqueous hydrazine solutions. The triazene species. [Gamma radiation]

Journal Article · Wed Apr 04 23:00:00 EST 1979 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100470a006· OSTI ID:6232368

Sutherland, J W

Pulse radiolysis of aqueous hydrazine solutions has been studied in the pH range 2 to 13. At times greater than about 1 ms after the pulse, a single transient species is observed (lambda/sub max/230nm). This species decayed by first-order kinetics under all conditions studied. A mechanism which accounts satisfactorily for the observed kinetic behavior is proposed. This species, identified as triazene (N/sub 3/H/sub 3/) is amphiprotic and the following acid--base equilibria are rapidly established: N/sub 3/H/sub 4//sup +/in equilibrium N/sub 3/H/sub 3//sup +/H/sup +/ (pK/sub 1/ = 4.95, ..delta..H/sub 1//sup 0/ = -4.9 kcal mol/sup -1/, ..delta..S/sub 1//sup 0/ = -39.2 eu) N/sub 3/H/sub 3/in equilibrium N/sub 3/H/sub 2//sup -/ + H/sup +/ or N/sub 3/H/sub 3/ + OH/sup -/ = N/sub 3/H/sub 4/O/sup -/ (pK/sub 2/ = 11.37, ..delta..H/sub 2//sup 0/ = -4.2 kcal mol/sup -1/, ..delta..S/sub 2//sup 0/ = -67 eu). pK values derived from the dependence of the first-order rate constant on pH, from the dependence of initial absorbance on pH, and from the dependence of the first-order rate constant on temperature at selected values of pH are in satisfactory agreement. The rate constants for decomposition of the acidic and basic forms of triazene are k/sub N3H4/sup +// = 1.97 X 10/sup 11/ exp(-12600/RT)s/sup -1/ and k/sub N3H2/sup -// = 2.14 X 10/sup 14/. exp(-19200/RT)s/sup -1/. For N/sub 3/H/sub 3/, which is stable relative to the faster reaction rates of its conjugate acid and base forms, k is estimated to be less than or equal to 0.001 s/sup -1/ at 24/sup 0/C. The dependence of the observed first-order rate constant on pH at constant temperature is expressed by the following equation: k/sub obsd/ = (k/sub 3//(1 + (K/sub 1//(H/sup +/)))) + (k;/sub 4//(1 + ((H/sup +/)/K/sub 2/))) (k/sub 3/ = k/sub N3H4/sup +// = 133 s/sup -1/, k/sub 4/ = k/sub N3H2/sup -// = 2 s/sup -1/, pK/sub 1/ = 4.9/sub 5/ and pK/sub 2/ = 11.3/sub 7/). Phosphate is a catalyst for the decomposition of triazene. It is shown that the conjugate acid of neutral triazene has unit positive charge and its conjugate base has unit negative charge.

• Research Organization: Brookhaven National Lab., Upton, NY
• OSTI ID: 6232368
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 83:7; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
AQUEOUS SOLUTIONS
AZINES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DATA FORMS
DECOMPOSITION
DISPERSIONS
ELECTROMAGNETIC RADIATION
EXPERIMENTAL DATA
GAMMA RADIATION
HETEROCYCLIC COMPOUNDS
HYDRAZINE
INFORMATION
IONIZING RADIATIONS
ISOLATED VALUES
KINETICS
MIXTURES
NITROGEN COMPOUNDS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
RADIOLYSIS
REACTION KINETICS
SOLUTIONS
TRIAZINES