T}IE
KINETICS
OF OXYGEN
EXCHANGE
BETWEEN
THE
SULF]TE
TON
AND WATER
A
Thesis
submitted
to
the
Faculty
of
Grad.uate
Studies
and
Unlversity of
Manitoba
fn Partial
F\.¡.lfil}ment
the
Requirements
for
the
De.c'ree
MASIER
01¡
SC]BNCH
by
Roiralcl Henry
Voss
August L969
Research
of
c
Ronal-d
Henry
Voss
t969.
to
my
parents
ACKNOWIEDGEn/IENTS
I
am
pl-eased.
to
aclcnowl-edge
my
gratitude to
Dro
RoH"
Betts
for
his
constructive
ad.vice
and
guÍdance
during
the
course
of
this
research;
to
my fetlow
workeru Steve T-,ibich,
for
the
numerous
d,iscussions
with him;
and to
the National
Research
Corrncil
and,
the
Ðepartment
of
Chemistry
for
the financial
assistance
in
the
form
of
a
scholarship
and a
demonstratorship
respectively"
-D4/
2,/,
^
/l
/f.
Ue'a-¡¿-z
R"H"
Voss
ABSTRACT
Oxygen
of
mass
18
was
used
as a stable tracer
to
measure the rate of exchange between
the
sulfite ion and"
water as a function of
pH
and
total- sulfite concentration"
A
value for the rate consta.:rt
of hydration
of S0,
in
aqueous
sol-ution
was
d.etermined
"
The
gross
rate
constants
kt
and
k_, for the overall
reaction
tt* rvnn
-
n
+
Hùu3
Äì
I
---i-
ß<-
11'
-r
S0r+ HrO
-o^
at
24"7"C and. ionic
strength
=
0"$
were
eval-uated
from
exchange
results to be
k.
=
2,48 t
o"27 x
109
mole-f l-,
="".-f
I
k
..,
=
1"06
t
o"f3 x lo8
"""u-1
and are one to two
orders of magnitude larger than the
values
determined from
rel-axation measurements made earlier
on this
system
by other workers"
Alsou
for the first
time,
rate constants
for the
k2
=
7
"00
t 0"21
x 102
mole-l
l-"
""""-f
k-2=
1 sec"-r
at 24"7oC and- ionic
strength
=
0"9"
pyrosulf
ite
equil-ibripm
-k2
2
HSO
J
kìp
¿) ¿
were obtained
CONIENTS
TNTRODUCTION
1
-
1
Isotopic
exchange reactions
e o o e o
ø
L
-
2
Mathematics
of
exchange reactions
o o o
I
-
3
Use
of
OfB"
"
è
o o
ô
o
@ e s o o o o
o
1
-
4
ll!"ry
study
the rate
of exchange?
o o o
ô
I-5Sornesystemsstud.ied-"
"
6
o o
e e e e o
Oxygen
exchange betweenc
(i)
chromium
(Vf)
oxyanions
and water"
(ii)
bromate,
chlorateu and
iodate
ions
(iii)
sulfate ion and
water"
.t:o"*?"T":
(iv)
perrhenate
ion
and-
water
o
e
@ ø o
(")
carbonate and" bicarbonate
ions and
water
"
6
qualitative
rules for
exchange"
"
ø o o
-
7
The SO^
-
H^0 system
¿¿
(i)
nature
of the
species
present"
, o
(ii)
review of
0fö exchange-reactions
o 6 ø
(iii)kinetic
stud,ies.
"
o o o ø o
o
q
o o ø
PURPOSEOFTHEIN\TESTIGATION"
"
ø
O O O O O
O O ø
EXPERTMENTAL
3
-
t
Matgriais
o
o e e o 6
o
o
o s o
ø ø o o
o o
3-2Samplepreparation"
o E o
o ø o
e e
ø
o o o
3
-
3
Isotopic
analysis
o
o
e o ô o
o
6
ø o o
@
o
3
-
4
Treatment
of the
data
o
ø e o
o o ø ø
o
o
o
Page
't
6¿
,2
^
a
t/
14
00
oo
¿¿
2B
t5
1B
20
1
I
1
I
¿
J
/9
?6
2ñ
40
¿-1
AA
49