The pulse radiolysis of deaerated aqueous bromide solutions

M. S. Matheson; W. A. Mulac; J. L. Weeks; J. Rabani

doi:10.1021/j100879a004

The pulse radiolysis of deaerated aqueous bromide solutions

M. S. Matheson^*, W. A. Mulac, J. L. Weeks, J. Rabani

^*Corresponding author for this work

Institute of Chemistry

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Abstract

The pulse radiolysis of deaerated aqueous KBr solutions in the pH range 5 to 9 yielded k(OH + Br^-) = (1.2 ± 0.15) × 10⁹ M^-1 sec^-1, 2k(Br₂^- + Br₂^-) = (3.3 ± 1.0) × 10⁹ M^-1 sec^-1, and k(e_aq^- + Br₂^-) = (1.3 ± 0.5) × 10¹⁰ M^-1 sec^-1. The value of k(OH + Br^-) increases at low pH values and decreases markedly at high pH, indicating that the transition complex BrOH^- may react with H₃O⁺. The molar extinction coefficient of Br₂^- at 3650 A is 7800 ± 2000 M^-1 cm^-1. The k(OH + Br^-) value has been compared with other rate constants for OH by means of rate constant ratios in the literature. Relative rate constants involving k(OH + Br^-) must be used cautiously because of the pH sensitivity of this rate constant.

Original language	English
Pages (from-to)	2092-2099
Number of pages	8
Journal	Journal of Physical Chemistry
Volume	70
Issue number	7
DOIs	https://doi.org/10.1021/j100879a004
State	Published - 1966

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title = "The pulse radiolysis of deaerated aqueous bromide solutions",

abstract = "The pulse radiolysis of deaerated aqueous KBr solutions in the pH range 5 to 9 yielded k(OH + Br-) = (1.2 ± 0.15) × 109 M-1 sec-1, 2k(Br2- + Br2-) = (3.3 ± 1.0) × 109 M-1 sec-1, and k(eaq- + Br2-) = (1.3 ± 0.5) × 1010 M-1 sec-1. The value of k(OH + Br-) increases at low pH values and decreases markedly at high pH, indicating that the transition complex BrOH- may react with H3O+. The molar extinction coefficient of Br2- at 3650 A is 7800 ± 2000 M-1 cm-1. The k(OH + Br-) value has been compared with other rate constants for OH by means of rate constant ratios in the literature. Relative rate constants involving k(OH + Br-) must be used cautiously because of the pH sensitivity of this rate constant.",

author = "Matheson, {M. S.} and Mulac, {W. A.} and Weeks, {J. L.} and J. Rabani",

year = "1966",

doi = "10.1021/j100879a004",

language = "אנגלית",

volume = "70",

pages = "2092--2099",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "American Chemical Society",

number = "7",

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TY - JOUR

T1 - The pulse radiolysis of deaerated aqueous bromide solutions

AU - Matheson, M. S.

AU - Mulac, W. A.

AU - Weeks, J. L.

AU - Rabani, J.

PY - 1966

Y1 - 1966

N2 - The pulse radiolysis of deaerated aqueous KBr solutions in the pH range 5 to 9 yielded k(OH + Br-) = (1.2 ± 0.15) × 109 M-1 sec-1, 2k(Br2- + Br2-) = (3.3 ± 1.0) × 109 M-1 sec-1, and k(eaq- + Br2-) = (1.3 ± 0.5) × 1010 M-1 sec-1. The value of k(OH + Br-) increases at low pH values and decreases markedly at high pH, indicating that the transition complex BrOH- may react with H3O+. The molar extinction coefficient of Br2- at 3650 A is 7800 ± 2000 M-1 cm-1. The k(OH + Br-) value has been compared with other rate constants for OH by means of rate constant ratios in the literature. Relative rate constants involving k(OH + Br-) must be used cautiously because of the pH sensitivity of this rate constant.

AB - The pulse radiolysis of deaerated aqueous KBr solutions in the pH range 5 to 9 yielded k(OH + Br-) = (1.2 ± 0.15) × 109 M-1 sec-1, 2k(Br2- + Br2-) = (3.3 ± 1.0) × 109 M-1 sec-1, and k(eaq- + Br2-) = (1.3 ± 0.5) × 1010 M-1 sec-1. The value of k(OH + Br-) increases at low pH values and decreases markedly at high pH, indicating that the transition complex BrOH- may react with H3O+. The molar extinction coefficient of Br2- at 3650 A is 7800 ± 2000 M-1 cm-1. The k(OH + Br-) value has been compared with other rate constants for OH by means of rate constant ratios in the literature. Relative rate constants involving k(OH + Br-) must be used cautiously because of the pH sensitivity of this rate constant.

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SN - 0022-3654

VL - 70

SP - 2092

EP - 2099

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 7

ER -

The pulse radiolysis of deaerated aqueous bromide solutions

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