Abstract
Nitrous oxide has been used as a specific scavenger of aquated electrons produced by photo-detachment from Fe
2+
aq.
(
hv
→Fe
3+
aq.
+ e¯
aq.
) and Fe(CN)
4–
6
(
hv
→ Fe(CN)
3–
6
+ e¯
aq.
) by light of wavelength 2537 Å. In each case
Ф
(N
2
) increases to a limiting value as [N
2
O] is increased; it is 0·07 for the former process and 0·66 for the latter. Use of isopropanol instead of N
2
O in the latter case indicated that
no
H atoms are formed in the primary act. Competition experiments indicate that
k
(e¯
aq.
+ H
+
) /
k
(e¯
aq.
+ N
2
O) =1·86 ± 0·12 when Fe
2+
aq.
is used as the electron source and 1·55 ± 0·1 when lanthanum ferrocyanide is used. For the K
4
Fe(CN)
6
solutions, 2
Ф
(N
2
)=
Ф
(Fe(CN)
3–
6
) unless KCN is present when OH+CN¯→OH¯+CN and Fe(CN)
3–
6
+ CN → C
2
N
2
+ Fe(CN)
5
H
2
O
3¯
(+CN¯→ Fe(CN)
4¯
6
+ H
2
O) occur. The slopes of the Brønsted-Bjerrum plot for log
10
k
(e¯
aq.
+ NO¯
2
) is much larger (2 to 2·7) than expected or is obtained from radiation chemical experiments and is explained by a model in which e¯
aq.
reacts with NO¯
2
while still within the relaxed ion atmosphere of the ferrocyanide ion. Other experimental and theoretical evidence is added in support of this hypothesis.
Cited by
80 articles.
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