(College of Chemistry and Environmental Science, Hebei University, Baoding 071002, China)
Received on Oct. 11, 2005.
Abstract The kinetics and mechanism of iridium(III) catalyzed oxidation of methanol by cerium(IV) in sulfuric acid media has been investigated by titrimetric technique in the temperature range of 25 - 40ºC. The reaction order of [Ce(IV)] was found to be unity, and that in both methanol and iridium(III) to be positive fractional. It was found that the pseudo first order ([CH3OH]＞＞[Ce(IV)]) rate constant kobs increases with the increase of [H+], but decreases with the increase of . Under the protection of nitrogen, the reaction system can not induce polymerization of acrylonitrile indicating no free radicals generated. On the basis of the experimental results, a suitable mechanism has been proposed. From the hydrogensulfate dependence, Ce(SO4)2 has been found as the kinetically active species. The preequilibrium constants, composite rate constants together with the parameters were evaluated.
Keywords Iridium(III) ion, cerium(IV) ion, methanol, catalyst, kinetics and mechanism
Ceric sulfate, ferrous ammonium sulfate, methanol and iridium trichloride were of A.R. grade. Twice distilled water was employed throughout the experiment. Ceric sulfate solution was prepared by warming it in sulfuric acid and standardized with ferrous ammonium sulfate using ferroin as an indicator. Methanol was purified by distillation and its concentration was obtained from its density measurements. Stock solution of iridium trichloride was prepared by dissolving in warm 1.0 mol·dm-3 HCl solution and kept for several days at about 40ºC to attain the equilibrium. The concentration of iridium(III) in the stock solution was determined spectrophotometrically. The ionic strength was maintained by adding KNO3 solution.
2.2 Procedure and kinetic measurements
Under the condition of [CH3OH]>>[Ce(IV)]>>[Ir(III)], 25ml of solution containing definite [Ce(IV)], [Ir(III)], [H2SO4] and [KNO3], and 25ml of methanol solution of appropriate concentration were transferred separately to the upper and lower branch tubes of l type two-cell reactor. After it was thermally equilibrated in a thermostat, the solutions were thoroughly mixed. The progress of the reaction was monitored by withdrawing aliquots of the reaction mixture at regular intervals, quenching the reaction by adding to excess standard ammonium.iron(II) sulfate solution in sulfuric acid and back-titrating the unreacted iron(II) against standard cerium(IV) using ferroin as indicator. The pseudo-first order rate constants kobs were evaluated (Figure 1) from the slope of the plots of ln[Ce(IV)]t versus time (t) i.e. ln((V∞-Vt) versus t where V∞ and Vt devote the volume of standard cerium (IV) solution needed in back titration for the unconsumed iron(II) solution at infinity and time(t) respectively. To evaluate kobs, generally 8-10 values at least up to 80% completion of the reaction were used. Average values of at least two independent determinations of kobs were taken for analysis. The observed rate constants were reproducible within the experimental error 5%.
Fig.1 Plots of ln (V∞-Vt) vs. t at 30ºC
[Ce(IV)] = 2.0×10-3mol·dm-3, [CH3OH] = 0.05mol·dm-3, [H2SO4] = 0.5mol·dm-3, m= 1.0mol·dm-3.
A ([Ir(III)] = 0 mol·dm-3); B ([Ir(III)] = 4.0×10-7 mol·dm-3).
3 RESULTS AND DISCUSSIONS
Under the condition [CH3OH]>>[Ce(IV)]>>[Ir(III)], the plot of ln (V∞-Vt) versus time t was linear(Figure.1), indicating that the reaction is first order with respect to [Ce(IV)]. The pseudo first order rate constants kobs are independent upon the initial concentration of cerium (IV) in the 2 - 4.5 ×10-3mol·dm-3 range. The dependence is given by:
3.2 Dependence on [CH3OH]
At fixed [Ce(IV)], [Ir(III)], [H2SO4], ionic strength (m) and temperature, kobs increases with the increase of [CH3OH]. The plot of kobs vs.[CH3OH] was a smooth curve passing through the origin indicating fractional order in [CH3OH] (observed reaction order nap = 0.2 ). The plot of 1/kobs vs. 1/[CH3OH] exhibits excellent linearity (Figure.2) with a positive intercept and slop.
Fig.2 Plot of 1/kobs vs. 1/[CH3OH] at 30ºC
[Ce(IV)] = 2.0×10-3mol·dm-3，[Ir(III)] = 4.0×10-7mol·dm-3,
[H2SO4] = 0.5mol·dm-3, m= 1.0mol·dm-3.
3.3 Dependence on [Ir(III)]
The fact that under the experimental conditions in the absence of Ir(III) ions the reaction practically does not take place is supported by an independent experiment ( Figure.1. A). Addition of traces of Ir(III) enhances the rate significantly (Figure 1. B), kobs shows the fractional order in [Ir(III)] (na p = 0.56-0.69), 1/kobs vs. 1/ [Ir(III)] yielded good linear plots (Figure 3) with a positive intercepts and slops at different temperatures. The kinetic data also fit well with Michaelis-Menten Plot.
Fig.3 Plots of 1/kobs vs. 1/[Ir(III)] at different temperatures
[Ce(IV)] = 2.0×10-3mol·dm-3, [CH3OH] = 0.05mol·dm-3,
[H2SO4] = 0.5mol·dm-3, m = 1.0mol·dm-3. 3.4 Dependence on 
 was varied over the range (0.2-1.0 ) mol·dm-3 at fixed [H+] ([H+] = 1.0 mol·dm-3≈[HClO4]+[H2SO4]), [CH3OH] and [Ir(III)],  was calculated ignoring the dissociation of in the presence of fairly high [HClO4]. This leads to ≈[H2SO4]. Here  shows a rate retarding effect ( nap = -0.70 ) and the plot of 1/ kobs against  was found to be linear (regression coefficient r = 0.997) with positive intercept and slope (Figure 4). Thus the hydrogensulfate dependence can be represented as follows: (1)
where a, b and c are constants under the experiment conditions.
Fig. 4 Plot of 1/kobsvs.  at 30ºC
[Ce(IV)] = 2.0×10-3mol·dm-3, [CH3OH] = 0.05mol·dm-3,
[Ir(III)] = 4.0×10-7mol·dm-3, m= 1.0mol·dm-3.
3.5 Dependence on [H+]
mol·dm-3, [Ir(III)]= 4.0×10-7 mol·dm-3,
The completion of the reaction was marked by the complete fading of Ce(IV) color (yellow). The reaction product as formaldehyde was detected by spot test and estimated gravimetrically as its 2, 4, dinitrophenylhydrazone derivative. It was found that the reaction is of 1:1 type. Another product Ce(III) was also detected by spot test.
3.7 Acrylonitrile polymerization test
Acrylonitrile solution(40%,V/V) was added to the reaction mixture under the protection of nitrogen gas the reaction system can not initiate any polymerization of acrylonitrile indicating no free radical generated in the reaction.
3.8 Mechanism of the reaction
The kinetic data (i.e.1/kobs vs.1/[CH3OH]) fit well with Michaelis-Menten type model suggests that CH3OH is involved in the reversible formation of a complex between the oxidant and the substrate, and the kinetic data (i.e.1/kobs vs.1/ [Ir(III)]) also fit well with Michaelis-Menten type model indicates a probable way of association of Ir(III) and the complex formed in the first preequilibrium step. Ce(SO4)2 has been found kinetically active in this study. Thus a mechanism consistent with the found kinetic characteristics is presented as follows:
From the mass balance relationship we have:
Subscripts T and e stand for total and equilibrium concentration respectively , f gives the fraction of the total cerium(IV) kinetically active.
From step (4) of the above mechanism the rate of disappearance of [Ce (IV)]T can be written as:
The other two forms of
Eq.(8) are as follows:
Table 2 Rate constants and activation parameters
* r = 0.99, B = -7449, A = 21.32 for the linear regression of ln kn vs.1/TThe second equilibrium probably involves the outersphere association of the species(I) and catalyst followed by the electron transfer leading to the species(II) which may be Ce(III)·(CH3OH)·Ir(IV), subsequently electron transfer occurs within the complex to give Ir(III) and the free radical which is rapidly oxidized by Ce(IV) at a fast step. Thus the oxidation of methanol occurs through the Ir(III)/Ir(IV) catalytic cycle. 3.9 Kinetically active Ce(IV) species and  dependence
Under the experimental conditions in aqueous sulfuric acid medium, the important cerium(IV)-sulfato complexes are Ce(SO4)2+ , Ce(SO4)2 and HCe(SO4) and the relevant equilibrium[12,13] are:
+ Ce(SO4)2 + H+ (12)
Ce(SO4)2 + HCe(SO4) b3 = 3.4 (13) Among the different sulfato species, the kinetically active species can be inferred on the basis of kinetic data, not inferring it according to the magnitude of concentration. From the relation between hydrogensulfate and kobs, Ce(SO4)2 has been found as the kinetically active species in the present study. The concentration of Ce(SO4)2 can be approximately obtained. The following Eqs. can be derived from Eqs.(11)-(13):
Substituting above Eqs. into Eq.(14) we get:
By considering the relative magnitudes of the successive formation equilibrium constants which are in the order 1>>2>>3, the value of are much less than two terms later. Therefore, we get Eq.(16) from Eq.(15). (16) (17) Substituting Eq.(17）into Eq.(8）we get: (18)
Eq.(19) can be derived from Eq.(18) after rearrangement:
Eq.(19) is the same as Eq.(1) and can explain well negative number order (na p= - 0.70) dependence on . Eq.(20) suggests that 1/ kobs vs. should be linear, and was evidenced in Figure 4. b3( 6.66 ) from the ratio of slop to intercept of line in Figure 4 was estimated and is in good agreement with the previously reported value[12,13]. All above show that Ce(SO4)2 is the kinetically active species indeed.
Because of the existence of so many protondependent equilibria among the reactants, the quantitative interpretation of [H+] dependence is very much complicated and uncertain. Because of this complexity in the present system, no attempt was made to explain the observed [H+] dependence from the proposed reaction mechanism. However, the qualitative observation is in agreement with the fact that cerium(IV) oxidation reaction in aqueous sulfuric acid media are acid catalyzed. On protonation, positive charge on the cerium(IV) sulfato species increases and it facilitates the electron transfer towards cerium(IV) center.