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that the first -order reaction is not observed in water and that it dis-
appears in a solvent mixture of 70% DMSO /30% H2O.
The values of kb exhibit a positive salt effect which seems to
be dependent on total cation concentration rather than ionic strength.
The data were found to fit the equation
by
BRUCE BURNS
A THESIS
submitted to
OREGON STATE UNIVERSITY
in partial fulfillment of
the requirements for the
degree of
MASTER OF SCIENCE
June 1966
APPROVED:
I. INTRODUCTION 1
II, EXPERIMENTAL 12
General . . 12
Apparatus 13
Reagents 14
Experimental Procedure 17
Runs in which Persulfate was Analyzed 17
Runs in which Absorbing Species (I or Ce +4 )
3
were Analyzed 18
Calibration of DU 24
Treatment of Data 24
Mechanism 33
The Effect of Oxygen 38
Effect of Added Cations 43
Solvent Effects 54
Effect on kb 54
Solvent Mixtures 56
Catalytic Effect of Chloride 58
Effect of Allyl Acetate 60
The Reaction of Per sulfate and Cerous Ions . , 60
IV, CONCLUSIONS 62
BIBLIOGRAPHY 64
LIST OF FIGURES
Figures Page
Plot of Ro/ S2082 vs. [I ]for calculations of
1
la. I
3. Log kb vs [K+;1 45
4. kb in DMSO vs. total potassium ion 46
5. Log kb in DMSO vs. square root of ionic
strength 47
l
6. Plots of Ro/ S2082 vs. [I ] for various H2O
]
-DMSO mixtures (100% -O, 85.00% -0,
70.00% -, 50, 00% -®DMSO by weight). . . 57
LIST OF TABLES
Table Page
I Data on Rate variation with LIJ at various
ionic strengths 25 -26
I. INTRODUCTION
agent (E = 2.01 volts) yet many of its reactions are so slow that they
0
The kinetics of this reaction were first studied by Price (28) in 1898
who observed a reduction in rate constant with time due to the form-
ation of the triiodide ion as the reaction progressed. In recent years
increased ion pairing between the reactant anions and added cations
over what might be expected in water. In addition, studying the
reaction in mixtures of water and DMSO would provide a means of
isolating specific solvent influences which are bound to be present in
an aprotic solvent. From preliminary investigations it was apparent
that the reaction was zero or near zero order in iodide ion although
affect the rate of the reaction but with an order less than one. This
indicated that the persulfate- iodide reaction in DMSO had a two term
rate law just as the persulfate- bromide reaction has in aqueous so-
lution (9, p. 182). In a later section it will be shown that a mecha-
nism can be written which leads to a rate law consistent with the
data and which involves a thermal decomposition step for persulfate.
The data obtained in this study for the persulfate- iodide reac-
tion have brought several facts to light which are focused in three
different manner than in water. These are the three factors which
differentiate these results from those obtained in aqueous solution.
Thus, any conclusions to be drawn about solvent effects of this
via two paths, one of which is catalyzed, the rate law being
Rate = -dS2082 /dt = kl +k2IH1IIS2O82] (23), Several steps have
been proposed as the initial and rate determining step for the un-
Reactions (2a) and (2b) provide paths for the exchange of sulfur
S2082
between and S35 labeled SO42 The mechanism for (2a)
SO4 + S*04
-
.
involves the entirely reasonable equilibrium
S042- + S*04. ,
4
No such exchange has been observed (7, 29), and, thus, these steps
are considered unlikely.
This initiating step (reaction 2) may also be brought about by
Presumably, the S041- radical itself exhibits this same effect, yet
this premise has not been verified (12).
House (12) has written a general mechanism for persulfate
k
2
-. 2SO4 slow (2)
2 -]
tx
dl
_ (k1+k3[x7]
ss) 1520821
where x2 is the substrate, x is its reduced form and {x7]
ss is
the steady state concentration of the intermediate substrate radical.
all 52082- reactions which are zero -order in the reducting agent
oxygen was observed to have no effect on the reaction which lends
some support to the premise that the reaction does not have a
radical chain mechanism.
The authors did not propose a mechanism for the reaction
k
1
S2082----g. 2SO4: (2)
(C H5 )S(0)O
2
+ SO
4
" : -4 SO42- + (C2H5)2S(0)O ó
(9)
-dDMSO
The rate law is
dt
(kl +k3 R) S2082- consistent
I
Elimination of reaction (8) would break the chain and the rate law
would reduce to kl S2082 1. But the authors determined the rate
persulfate in water. They gave the rate determining step for the
acid catalyzed reaction as
HS2O8 --a. SO4+ HSO4- (10)
Mechanism
This reaction falls into a different class from the first -order
Three mechanisms have been proposed to account for its first -order
dependence on iodide and persulfate:
Reference
52082 + I -a IS2083- slow (28) (11)
82083
IS2083 -a I' + slow (31) (12a)
3
+I- -0,.. 2SO4- + I' fast (12b)
ance in this laboratory centers around the fact that it has as a rate
Salt Effects
Húckel limiting law gives the relationship between rate constant and
strengths. King and Jacobs (20) found that the rate constants agree
with those predicted by the approximate form of equation (14) up to
ions were present log k was -1.06. While these values are in
0
near agreement there may be some significance in their differences.
Negative deviations from the limiting expression were observed
with MgSO4present ata= 0.06. Since it inherently contains all
and S imonson (25) derived an equation which fits data for several
reactions between ions of like charge. The equation is
1 " K(x)
k
k = ka 1 +K(x) + 1 +K(x) (15)
k = F k (17)
0
where .7A
,
TB , and/ are the activity coefficients of each
reactant and the activated complex.
Olson and Simonson interpret the two terms in the brackets
Perlmutter- Hayman and Stein (27) have fit their data on the
cation present. This equation fit their curves from very low values
II. EXPERIMENTAL
General
stock solutions or solutions for kinetic runs were cleaned with di-
chromic acid cleaning solution and rinsed many times with distilled
water. Most glassware was oven dried at 1100C.
13
Apparatus
mately 10" x 12" x 18" fitted with a pump which circulated water
through the jacket around the sample holder in the spectrophotometer,
a 250 watt blade heater and thermoregulator set at 19.80 + 0. 03°C.
Both baths were cooled by three turn coils of copper tubing at the
bottom through which flowed ordinary tap water. The coolant water
for the second bath was pre -run through about 10 feet of copper tubing
coiled inside a small crock filled with ice water. This procedure was
necessary in the summer since the tap water was 22oC, but was not
uously during the time the instrument was on at ca 2. 5 amp but only
14
a trickle (a few tenths of an amp) when the instrument was off. The
instrument was operated at 6.4 volts.
Reagents
to the pressure obtained from the water aspirator (70- 85 °C). Start-
ing with about one liter of unpurified DMSO a middle fraction of 500
necked standard taper joint flask. A ground glass stopper was fitted
in the center neck. In one side neck was fitted a gas inlet tube which
reached to the bottom of the flask and was connected to a length of
Tygon tubing with a pinch clamp. The other side neck was fitted
with a gas inlet tube broken near the top so that it did not reach the
with nitrogen. In this way the solution was protected from contact
with the air and the titer changed very little from day to day.
allyl alcohol and allowing the mixture to reflux for a few minutes.
Then water was added to destroy the excess acetyl chloride. The
organic layer was separated and extracted with two portions of 10%
16
chloride and allowed to stand overnight. The liquid was poured off
1:5 nitric acid. At this point there were about 15 grams of cerous
nitrate dissolved in about 10 ml of water containing nitric acid. Re-
peated attempts to remove the nitric acid by boiling proved quite
futile so an unboiled sample was simply mixed with an equal volume
of double distilled DMSO, placed in vacuum dessicator over P2O5
which was pumped down with an aspirator, closed off, and left for
three days. After this time the sample had crystallized into color-
less crystals. The crystals were broken up and spread on a petrie
dish after which the desiccator was again pumped down and left for
several more days. At this point the crystals seemed "dry ". The
17
solid was always handled in a dry bag filled with dry nitrogen until
a sample was weighed into a small, dry stoppered volumetric flask
anddissolved in DMSO. Two solid samples were analyzed by oxidiz-
ing the Ce(III) and DMSO by boiling with K2S2O8 in excess and back
Experimental Procedure
and, hence, were not done in the DU. The object of these runs was
time when half the pipet had emptied into the quench solution. The
either iodide or cerous ion both of which yield products which can be
analyzed by their absorption of light in the near U. V. -far visible
region. In these experiments the products were analyzed and it was
most convenient to allow the reaction to procede right in the quartz
19
In some earlier runs the K2S2O8 solution was weighed into the reac-
tion vessels, but in later runs the KI solution was weighed. All the
which was pipetted was in error by some small amount because they
were made up by weight and delivered by volume. Inherent in the
method is the assumption that the molarity and molality of these
solutions are equal. Since most stock solutions of K2S2O8 and KI
were .02 to . 03 M the error in this assumption is probably fairly
small (ca. 0.5 %). But the more concentrated solutions of KNO3
erally, this would affect the ionic strength so that the(,( values were
least accurate of all the concentrations. Unfortunately, these errors
20
flasks. After the initial reactant solution was weighed into the flasks
the required amount of KNO3 solution was pipetted from the 19. 67oC
thermostated bath. The flasks were then placed in the bath for 30
minutes and the second reactant solution added. Zero time for each
reaction was taken at the time when half of the second reactant so-
lution was added to the reaction flask. The flasks were then filled to
the mark with thermostated solvent (which always took less than 60
seconds) and carried to the DU where they were placed in the quartz
cells. The empty cells were always placed in the DU at least 30
minutes before the start of the reaction. Each solution was actually
out of the bath for two to two and a half minutes. Runs were made
case of other workers (19, 21, 28). Before making up the solutions
the solvent was swept out with dry nitrogen for 20 minutes to remove
any trace of oxygen. Oxygen interferes with the second -order re-
observed that solutions which stood for more than five hours tended
to give low results.
Several experiments were done with constant persulfate and
varying iodide concentrations at ionic strengths between 0. 02 and
0.06M These runs were done to obtain the basic rate law and the
to k . The fact that such plots did give a straight line with non -
a
zero intercept verifies the above rate law since the reaction has
been shown to be first -order in persulfate.
DMSO and water from 85.00 %to 50.00% DMSO by weight in order to
establish the effect of the DMSO on the reaction rate as a specific or
general one. These were done using exactly the same procedure as
23
the ones in pure DMSO but at only one total potassium ion concen-
Calibration of DU
were (0.8 to 3.0) x10 -5M. The final dilutions were made in 10 ml
volumetric flasks and diluted with spectroscopic grade DMSO which
was also 0. 05 M in KI. Thus, the high ratio of I to I2 assured
Treatment of Data
Table (I) and Figures (la) through (le) it is apparant that the data
are scattered. In most cases this scatter is probably attributable
to either the factors listed above affecting the rate of the first -order
reaction or by the presence of oxygen in the solution which reduces
Table I. Data on rate variation with I at various ionic strengths.
r
Run K2 S2O8tx 103M
ll
103M
J1.008 +K
otalx 103M ,(x 103M Roi [S208 sec -1
Run
1K 2
S O x 103
1
2 8; IM
KI; x 103M K+ x 103 M ;Ix 103M Ro/
0
{S20821 x 106 sec _1
L J.
J L
;
4 5
[I] x103M
Figure la, Plot of Rot 2082 vs. [I
jfor calculations
of kaand kbat constant
l ,U.= 0.0600 M.
O
o
L6
14
L2
6 7 8 9 IO II 12
[IJxIO3M
2
Figure lb. Plot of Ro S208 vs. {1]for calculation of ka and k at constant
(,(= 0.0500M.
4 5 IO
[I1xIo M
Figure lc, Plot of Ro/ Is 2082 1 us.II for calculation of ka and kb at constant
l
L
/J = 0.0400 M.
4 5 6 lo
[I]XIO3M
Figure id. Plot of Ro/ [5208 J vs. [I ] for calculation of ka and k at constant wo
a b 0
(,= 0.0300 M.
I.
0.4
0.2 .
o I 2 3 4 5 6 7 8 9 10
[ r]xiO3M
Figure le. Plot of R / {s2o2j vs. [(j for calculation of k a and k b at constant
0 g
k(= 0.0200 M.
32
that about half the points in each plot fall off the best straight line.
The lines were drawn by the method of least squares, those points
away from the line drawn by eye through the points. In figure 1 d
there are actually two straight lines of different slope and intercept
which could be drawn. The indicated line was selected as the "best"
because more points fell on it than the line of greater slope. The
points denoted by ft5 were not used in the least squares calculation.
The same procedure was used for the studies at other solvent compo-
sitions but the requirements were relaxed somewhat for the data in
85% DMSO because there were too many "borderline cases". In the
70% and 50% solvent mixtures so few points were available that they
all had to be used. The same is true of the runs done with Ba(NO3) 2
added.
33
Mechanism
DMSO by persulfate. The second and third produce triiodide and re-
sult in the two term rate law
but it must occur. Since the pure DMSO used in the various experi-
ments contained 0.03% water, only one water molecule was present
for every 1000 DMSO molecules. Since water is tightly bound to
DMSO in solution, as evidenced by their obviously high heat of mix-
ing as well as the non -ideal behavior of DMSO -H2O mixtures (5),
it is unlikely that any water molecules are available to react with the
52082
[KI]x 103M total 103M i((x 103M
Run Rox 107sec 1 Ro/ x lObsec 1
LKZSZO8]x103M o 08
5 12.28 -- L 24.56 36.84 0.680 5.53
10 93.2 186.4 279.6 5.50 5.96
11 77.4 36.8 181.6 269.0 2.80 3.63
35
rate law
I
-d[S22-
Ld 08 = k [s2082] (24)
1
dt
A radical chain might be propagated by introducing the step
k
03S0:S(0)(CH3)2+ S2082 -' SO42 + SO4T + O3SO-S(0)(CH3)2 (25)
the data available at present. It will be noted from Table II that the
O + O O+
I I I
oxosulfonium iodide has been observed (32) and the above formula-
1
S2082 I value were those of triiodide in water. Clearly the 12
spite of the fact that the usual second -order I -52082- reaction is
also occurring to some extent (the extent is small because the reac-
tion was done in the presence of atmospheric oxygen; an inhibitor
to one of two things: (1) the iodide ions and DMSO molecules are
competing for the sulfate radical ions or (2) the iodide ions are not
reacting directly with sulfate radical ions at all but are competing
with the sulfate radical ions for the DMSO derived radical inter-
I + I. -+ I2 (23)
Any solvent molecules which react with sulfate radical ions but do
not react with iodide are not significant since they produce no de-
tectable products.
2-
The third reaction is one in which I and S208 react directly.
The mechanism for this reaction in aqueous solution has already
2-
Ro= ka [S2082-] + kb I [s2c8 (21)
dt =
I I I I
s
values from Table IV plotted versus I I -I . The values for the rate
may be compared with the data from experiments 33, 35, 37 and 38
Run x10 [KIjx 103M [Klt 103M ,c{x 103M Ro/ {s2082} x 106 sec -1
otalx
13 A 1. 58 20. 2 42. 3 43. 9 2. 50
Run
[K252081x103M KI x101Vi [K
total 103M (x 103M R I
S2082 } x106 sec -1
I.6
1.4
§ 1.2
-
0
m I.0
U) 0. 8
o
cc0.6
0.4 -
Q2-
1
0 I 2 3 4 5 6 7
[I ]x103 M
Figure 2. Comparison of runs done with (0) and without (Q) nitrogen sweep at
(,( = 0. 0500 M.
42
the runs are thrown onto these values, and they are probably only
good to within + 10% in general. In particular, Figure 2 shows that
Ro/ [s2082
1
values from this table plotted versus I
I 1 for calcula-
l L
( x 103M
[Kitotal
x 104M kbx 104M lsec
b
1 kax107 sec
a
60. 0 55.0 1.55 4.47
50. 0 45.0 1.30 5.10
40. 0 35.0 1.10 7.52
30. 0 25.0 0. 862 5.43
20. 0 16.3 0. 662 8. 00
-2.780
-2.782
Log kb(inH2O)
O -2.784
N
39 C
4
a -2.786
.a as
J -2.788
szs 4.1
J
-2790
4.2
4.3 -2.792
4.4
2 3 4 5
3
f 2 3 4 5
x
tç,tai 10 M
[KJf
+ x 10 3
K total M
Figure 3. Log kb vs. [K},
total
actual values in DMSO from equation (15) in H2O
I.4
L2
w 1.0
;f 0.8
A
4d 0.6
0A
3 4
[K Jtotai X 103 M
Figure 4. kb in DMSO vs. total potassium ion.
-3.8
-39
-4.0
-41
42
CA
J -4
-44
-45
-4.
er than those usually expected to obey equation (14). Amis and Potts
(1) did obtain agreement with the approximate form of equation (25)
at values of .212 and above.
The value of of is related to dielectric constant and tempera-
Since the value ofp( in water at 25°C is equal to 0. 509 the value
(
48.9 x 293
=1.03
The values of D in water and DMSO being 80.4 (1) and 48.9 (30)
Run
(
jK2S208,x
;
-
3
10 M [Klj
tl
J
3
x10 M
(
iK
l
Ixl0 3
M Ba
++ 3
10 M R S2O8
2- 6
x 106 sec
-1
Ro
Run
65 0
K2S2O8x 103M
J
5.00 l
Klfx 103M
6.16
_
`K+totalx 103M [Et4Nlxlo3M
34.8 5.79
(
S2O82
1,
1.30
lObsec -1
kb=ko+a(C1)+b(C2)+c(C3)+.,. (28)
where a, El and c are empirical constants and C1, C2, C3 are con-
centrations of each cation present. Using the one value for kb with
added barium ion the equation becomes
There are two ways in which added cations may act to accele-
rate reactions between two anions. One, the so- called primary salt
effect, is due to the ionic atmospheres associated with the anions
before they react and after they have formed the activated complex.
This is the effect predicted in the Brynsted -Debye equation. A
the cation acts to retard the movement of the reactant anions through
the solution and prevent themfrom coming together to form the act-
renders the larger cations more effective (and more ideal) than the
smaller ones.
In DMSO, however, ion pairing is considerably more likely.
The large discrepency in the calculated and theoretical values of
the light of ion pairing also. For example, the pK values of the
dissociation constants for KC1O3 and Ba(C1O3)2 are -0.1 and 0.7
respectively (6, pp. 169 -170). These values give some indication
of the ions pairing tendencies of the two ions.
Table VI also includes Ro/ [52082_]values for three runs
containing added Et4 NC1O4. The results show that the added Et4N+
ion had no effect on the reaction rate. This result certainly con-
experiment the ionic strength was varied from 0.046 to 0.057 which,
though not a large variation, should have produced a noticeable rate
reaction at all but only the specific effect of something like ion
pairing. In other words, the linearity of log kb versus Vµ noted
above is coincidental.
The above results do not weaken the argument about ion pair-
+
ing. The Et4N ion has a very small ionic potential. It was chosen
the ion.
53
O-S-O-O-S-O -0-S-0-+O-S-0-
I I I I
unpaired
I 1 I 1
O O O O
O O O O
KO-S-O-O-S-O-
I
O-S-O.
I I I
paired KO S-O +
I I I I
O O O O
would serve to enhance the transition state and products. But with
one end of the ion paired this repulsion does not exist. But it is
tion of aqueous persulfate solutions, they found that, while the un-
catalyzed rate constant was unaffected by added salts, the acid cata-
lyzed rate constant exhibited a negative salt effect. This fact casts
some doubt on the ion pairing argument advanced above as a
54
Solvent Effects
Effect on kb
strength, but it is not exactly clear what the actual value was. If
the dielectric constant value for DMSO of 48. 9 is substituted into
100 times too high, and the (kb) in DMSO becomes 6 x 10 -4. This
value is about 20 times as great as the actual value obtained.
neutral molecules where the transition state does not rely much on
Solvent Mixtures
The data are of a qualitative nature, but it is still apparent that the
50°/
70%
Figure 6.
3 6
[I] x9
103
12 15 18
Plots of Ro/ [s2082J vs. [I, for various H2O -DMSO mixtures
(100% -G, 85.00% -0, 70.00% -I, 50.00% -®DMSO by weight).
58
mechanism comes from DMSO and that I does not react with
SO4_ directly.
effect on the second -order reaction which does not exist in aqueous
solution. To discover this effect, one experiment was done with
Ro/ 52082 are lower than those taken fromFigure lc which has
+]
the same [K value. This is due to two factors: (1) the data
total
in Table VII were obtained at 380 mg instead of 370 mil which was
the usual wavelength; (2) the chloride ions compete with iodide ions
Table II. Reduction of persulfate by DMSO and KI
for iodine molecules and the I2C1- ion has a lower Eo value than I3 -.
3
The second reason above also accounts for the slight drop in
pose.
Table VIII. The reduction of Ce (III) by per sulfate.
,( x 2M-1 sec
Ro/ S2O82 -lx Eo
1
Run [Kzszo82ixlo3M {Ce (III) x103M 103M
IV. CONCLUSION
nature of the rate law in sharp contrast to its strictly second -order
nature in water. This feature has already been discussed in some
detail and it is to be regretted that so little data is available with
which to determine more accurately the nature of the k reaction. It
a
seems that valuable answers could be obtained by isolating the products
of the persulfate decomposition in pure DMSO. Also more data is
needed on the relationship between solvent composition, ionic strength
and k
a
. Further study of the first -order reaction could yield valuable
information on the nature of all first -order persulfate oxidations.
The tentative conclusion that the second -order reaction is in-
fluenced by specific cations only and not by all cations generally, even
at these moderate ionic strengths,is one which is in need of further
verification. It is not surprising to find deviations from a frankly
limiting equation like the -Debye equation, but the fact that
tetraethylammonium ion had no effect at all on the rate is startling
indeed. It is unfortunate that more experiments were not done at
various concentrations of multivalent ions like Ba ++ or La + ++ to
firmly nail down the salt effect as being one of ionic strength or cation
concentration only.
Another feature is the slowness of the second -order reaction
63
must play some role in DMSO even with its moderate dielectric con-
stant, especially in the case of di -and trivalent cations.
'In general, DMSO isa satisfactory solvent in which to study
ionic reactions. DMSO has the advantage of having the highest dielec-
tric constant of any aprotic solvent. Most commonly employed water
soluble salts are soluble in DMSO to some extent. Exceptions to this
rule are chlorides, sulfates, and other salts containing anions of high
BIBLIOGRAPHY
19. Jette, Eric and Cecil V. King. The oxidation of iodide ion by
persulfate ion. I. The effect of tri - iodide formation on the
reaction velocity. Journal of the American Chemical Society
51: 1034 -1047. 1929.
26. Pederson, Kai Julius. The effect of metal ions on the rate of
decomposition of nitroacetic acid. Acta Chemica Scandinavica
3: 676 -696. 1949.