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b*
*e-mail: faria@iq.ufrj.br
-d[BrO3-]/dt = k[BrO3-][Br-][H+]2 +
+ k[BrO3-][Br-]2[H+] + k[BrO3-][Br-]2[H+]2
Introducion
Judson and Walker1 were the first to study the reaction
between bromate and bromide (equation 1) and concluded
that it follows a fourth-order rate law (equation 2).
BrO3- + 5Br- + 6H+ 3Br2 + 3H2O
(1)
-d[BrO3-]/dt = k[BrO3-][Br-][H+]2
(2)
(3)
776
Experimental Section
Results and Discussion
Analytical grade chemicals NaBrO3 (Riedel-deHan),
HClO4 (Merck), NaClO4 (Riedel-deHan; Vetec), and
NaBr (Grupo Qumica) were used without further
purification. Water used had 18 M resistivity and was
obtained by a Milli-Q Plus purification system.
Kinetics experiments were carried out by two methods.
The first method (to be assumed when not indicated)
employed the UV-Vis diode array spectrophotometer HP
8452-A and Suprasil standard quartz cuvette with 1.00 cm
optical path (Hellma 110-QS). After the reagents were
transferred to the cuvette using a fast delivering digital
pipette (Transferpette), the cuvette was closed tightly with
a round Teflon plug. The total volume of the solution in
the cuvette was 2.0-3.0 mL. The cuvette containing a 3 x 5
mm Teflon coated cylindrical stirring-bar was placed inside
a jacketed cuvette holder equipped with a water powered
magnetic stirrer. The stirring rate was about 900 rpm and
no vortices were observed inside the cuvette. Experimental
points were taken at each 0.1 s for the faster experiments.
The estimated dead time after mixing the reagents was
about 2 s. The second method was the stopped-flow
technique performed by the use of the Hi-Tech Dual Mixing
Microvolume Stopped-Flow SF-61DX2. For both methods
the temperature was maintained at 25.0 0.1 C by a
circulating bath and the ionic strength of all solutions was
adjusted with NaClO4.
The reaction was followed at = 446 nm that
corresponds to the isosbestic point of the mixture of Br2
and Br3- ( = 111 L mol-1 cm-1). The extinction coefficient
at the isosbestic point was obtained by fitting a second
degree polynomial to the experimental absorbance data for
Br2 and Br3- obtained by Raphael in 2 mol L-1 perchloric
acid solution11. Our value for the extinction coefficient
( = 111 L mol-1 cm-1) of the isosbestic point of Br2 and
Br3- is in the middle of the values found by Lengyel et.
0.4000
0.2000
0.1000
0.0800
0.0600
14.3600
7.213
3.802
2.816
2.250
0 /
(10-6 mol L-1s-1)
1.00 10-3
1.00 10-1
0.201
0.00500
0.0100
0.0150
0.0250
0.0500
0.0750
0.100
7.00 10-4
5.00 10-2
1.05
0.0361
0.0516
0.0734
0.0988
0.148
0.197
0.247
0.296
0.347
0.572
0.107
0.242
0.513
0.917
2.600
4.130
6.900
9.000
10.10
26.00
2.00 10-4
1.00 10-3
3.50
1.032
1.296
1.552
1.772
2.004
2.406
2.772
0.760
1.370
1.990
2.980
3.600
4.530
5.530
7.00 10-4
5.00 10-2
1.05
0.105
0.200
0.301
0.409
0.500
0.600
0.691
0.800
0.900
1.03
1.32( b)
4.49( b)
9.53 (b)
16.6 (b)0
27.8 (b)0
41.6 (b)0
55.3 (b)0
75.5 (b)0
98.0 (b)0
124 (b)
0.00467
0.01790
0.04700
0.11200
0.47300
1.07000
2.13000
Table 3. Slope of the linear fitting for the plots of log o p[H].
(T = 25.0 C).
[Br-]0/
mol L-1
I/
mol L-1
[H+]0/
mol L-1(a)
Slope log
0p[H]
-2.03 0.03
-2.01 0.06
-2.02 0.14
-2.02 0.03(b)
k1
k-1
k2
k-2
H2BrO3+ +
H+ + HBrO3
H+ +
Br- k3
BrO3
products
[ Br (V )][H + ]2
[ H + ]2 + K1[ H + ] + K1K 2
= k3 [H2BrO3+][Br-]
[BrO3-]0/
mol L-1
777
(4)
(5)
(6)
Using this scheme and considering that the ratedetermining step is reaction 6, the rate of reaction, , can be
given as a function of the total bromine(V) concentration.
(7)
(8)
(9)
(10)
(11)
(12)
(13)
778
0.12
0.08
0.36
0.18
0.40
Main Electrolyte
Ref.
HClO4, NaClO4
HBr, Mg(ClO4)2
H2SO4
HClO4, NaClO4
HClO4, NaClO4
HBr, NaClO4
HBr, Mg(ClO4)2
NaClO4
HClO4, NaClO4
HClO4, NaClO4
HBr, NaClO4
H2SO4
HBr, Mg(ClO4)2
HBr, Mg(ClO4)2
HClO4, NaClO4
HBr
HBr, Mg(ClO4)2
NaClO4
HBr, NaClO4
HClO4, NaClO4
HClO4, NaClO4
NaClO4
NaH2PO4/H3PO4 buffer
HBr, NaClO4
HClO4, NaClO4
4
5
3
this work
4
8
5
10
4
this work
8
3
5
5
4
1
5
10
8
this work
this work(a)
10
9
8
this work
(14)
HBrO3 + H+ = H2BrO3+
(15)
(16)
H2Br2O3 +
Br-
products
(17)
(18)
(19)
Ref.
17
18
19
Acknowledgments
This work was sponsored by Conselho Nacional de
Desenvolvimento Cientfico e Tecnolgico-CNPq,
Fundao de Amparo Pesquisa do Estado do Rio de
Janeiro-FAPERJ, Fundao Jos Bonifcio-FUJB,
Financiadora de Estudos e Projetos-FINEP and CEPG-UFRJ.
References
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36, 211.
3. Bray, W. C.; Davis, P. R. J. Am. Chem. Soc. 1930,
52, 1427.
4. Young; H. A.; Bray, W. C. J. Am. Chem. Soc. 1932,
54, 4284.
5. Bray, W. C.; Liebhafsky, H. A. J. Am. Chem. Soc.
1935, 57, 51.
6. Sclar, M.; Riesch, L. C. J. Am. Chem. Soc. 1936,
58, 667.
7. Clarke, J. R. J. Chem. Educ. 1970, 47, 775.
8. Domnguez, A.; Iglesias, E. Langmuir 1998, 14, 2677.
9. Rbai, Gy.; Bazsa, Gy.; Beck, M. T. Int. J. Chem.
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779