KINETICS AND MECHANISMS OF THE PYROLYSIS OF DIMETHYL ETHER

111. THE REACTION ACCELERATED BY HYDROGEN SULPHIDE

D. J. MCKENNEY AND K. J. LAIDLER
Department of Chemistry, University of Ottawa, Ottawa, Canada Received November 23. 1962 ABSTRACT The thermal decomposition of dimethyl ether in the presence of hydrogen sulphide was studied in the temperature range of 480 to 530' C, and over the pressure range of 5 to 500 mm of Hg. For a given pressure of dimethyl ether the rate of decomposition increased with the addition of increasing quantities of hydrogen sulphide, reaching a plateau after approximately 30% H S had been added. The relative rate of decomposition then remained constant until more than 50% HIS had been added. Further increase in the hydrogen sulphide concentration produced a linear increase in the relative rate. I n the region between 30 and 50Yo added HzS, the decomposition of ditnethyl ether was three-halves order with respect to ether pressure, and zero order with respect to hydrogen sulphide pressure. I n this region the three-halves-order cc1I2mole - ' I 2 sec-I. In the region rate constant can be expressed by k = 1.06X1014e-53,20Q'RT beyond 50% added HIS, the reaction was first order with respect to dimethyl ether, and onehalf order with respect to hydrogen sulphide. I n this region the three-halves-order rate constant cc1I2in01e-~1~ set-l. The experimental facts are shown is given by k = 4.98X 1014e-52,5001RT t o be consistent with a mechanism involving hydrosulphide radicals as the principal chain carriers. These H S radicals are produced mainly from the reaction of methyl radicals with hydrogen sulphide. The work leads to a value of 85.6 kcal for the dissociation energy of HIS into H SH.

Can. J. Chem. Downloaded from www.nrcresearchpress.com by 112.201.27.17 on 01/24/12 For personal use only.

+

INTRODUCTION

A number of workers (1-7) have suggested that thiyl radicals (RS) are more reactive than alkyl radicals. Thus thiols generally accelerate free-radical reactions involving saturated aldehydes; this has been shown to be the case in the liquid phase ( I ) , in photodecomposition reactions in the gas phase (2, 3) and in thermal decompositions in the gas phase (4-7). Birrell and co-workers (2) observed that various thiols (H2S, CH3SI-I, C2H6SH, etc.) catalyzed the photodecomposition of acetaldehyde, and in most cases the thiols increased the rate of the decomposition. The rates increased to a plateau with the addition of thiol and remained constant over a range of concentrations. When the thiol concentration was about three-quarters of the acetaldehyde concentration the relative rate (ratio of catalyzed to uncatalyzed rate) increased further. Hydrogen sulphide was found to be the most effective catalyst, and the catalytic effect decreased with increasing complexity of the thiol. The mechanism proposed for catalysis by methanethiol involved the chain transfer reaction
CH3

+ CH3SH

+

CH3S

+ CH, + CH3 + CO

followed by
CH3S

+ CH3CHO
2CH3S

+

CH3SH

and termination by
-+

CH3SSCHa.

Such a simple ~llechanism could not, however, explain the effects observed for other thiols. More recently Imai and Toyama have postulated mechanisms to explain the acceleration by hydrogen sulphide and methanethiol of the decomposition of acetaldehyde (4, 5, 7). The effect of hydrogen sulphide on the decomposition of dimethyl ether was also studied (6). These workers suggest that the catalytic effect of hydrogen sulphide is
Canadian Journal of Chemistry. Volume 41 (1963)

2009

The fact that there was an increase in relative rate a t very high pressures of H2S (>50% added HZ§) indicated that the mechanism postulated by Imai and Toyama (6) is not sufficient to describe the reaction completely. it was thought t h a t a mechanism similar t o inhibition mechanisms could be applied to the reaction accelerated by hj~drogensulphide. + CH20 + CH3 HS + HS . essentially due to reaction of methyl radicals with hydrogen sulphide. 41.products. J. T h e maximum amount of hydrogen sulphide which was added was approximately 67%. EXPERIMENTAL The apparatus used was essentially the same as described previously (8. the procedure described earlier (Part 111 being employed.2" C. maintained the tenlperature constant to about A0. The reaction vessel was a cylindrical quartz tube of about 250-in1 volume. .nrcresearchpress. and the results were found t o be fully reproducible over the entire range of pressure and temperature. so t h a t t h e inflection point occurred in all cases a t less than lOy0 decomposition. -+ CH3 --t Ill [241 PI] 1201 CHZO -t [31 la31 The rate equation to which this mechanism leads is and a three-halves-order dependence on ether concentration was obtained experimentally. + HS CH30CH3+ HS --+ H2S + CH3OCH2 CH30CH.with increasing concentration of hydrogen sulphide and reached a limit where further addition of hydrogen sulphide had no effect. as well as with the numbering in Parts I and 11 of this series. V O L . ccli2 The results led to a rate constant of k = 1. A Beclcman photopen recorder in conjunction with a quartz spiral gauge automatically recorded the pressure change as a function of time.17 on 01/24/12 For personal use only.2010 CANADIAN J O U R N I L O F CHEMISTRY. I t also seemed necessary t o extend the experimental investigation t o higher temperatures and higher pressures of H2S. 4 Thermo Electronic controller. Downloaded from www. see also Part I of this series). T h e reactants were mixed thoroughly prior to a run. set-l. The dimethyl ether and hydrogen sulphide were 99.com by 112. Rates were calculated from the slopes of the pressure-time curves a t the inflection point. Before each run the reaction vessel was pumped down to less than 10 p. This small residual pressure had no detectable effect on the rates. activated by means of a thermocouple in the copper furnace block. The induction period for the reaction in the presence of H2S was generally quite short.27. with the production of hydrosulphide (SH) radicals which in turn abstract hydrogen atoms from the substrate. Chem. and were used after three trap-to-trap distillations.82 X 1015e-512800iRT In the light of recent work (Part 11) in this laboratory on the action of inhibitors on the thermal decomposition of dimethyl ether. CH30CH. T h e temperature was measured by means of a thermocouple in the reaction vessel and a Thermo Electric Mini-Mite potentiometer.5% pure. These reactions are suggested to be faster than the reaction between methyl radicals and the substrate. The rates can therefore be considered to be initial rates to a very close approximation.201. For the thermal decomposition of dimethyl ether in the presence of hydrogen sulphide the rate increased . and the reactions were carried out over the temperature range of 360 to 440' C. *The numbering i s writfen so as to be consistent with the mechanism postulated below. T h e mechanism suggested for the reaction in the presence of sufficient hydrogen sulphide to ensure "liiniting" acceleration was as follows:" + CH30 + H2S CHZOH + HS CH3 + H2S CH. 1963 Can. The details of this arrangement have been described by Laidler and Wojciechowslri (8).

In this region the order with respect to hydrogen sulphide is obviously zero.2. A plot of relative rate (i. 520. and X 480' C. FIG. and with about 75 to 99% added H S . The curves drawn have been calculated from Fig. the shorter the plateau. Downloaded from www. although there appears to be a slight increase withdecreasing temperature. 0 520" C. 3. 2) shows this dependence more clearly. 1 that the length of the plateau depends on the pressure of ether. and was therefore ignored.27. A typical pressure-time curve is shown in Fig.com by 112. 2. This result differs from that found in the nitric oxide inhibited decomposition of dimethyl ether (Part 11). R e l a h e rate (v/vo) against the percentage of hydrogen sulphide for three different temperatures: A 530" C. to be considered later. I t mas found t h a t the total pressure decreased by approximately 1% to a limit. and 0 20 mm of ether. 2 . 111 2011 RESULTS Can. Curve A is an actual tracing of the record obtained for the decomposition of 90 mm of dimethyl ether in the absence of H2S. The solid lines have been calculated from Fig. For a given pressure of ether the relative rate increases to a plateau with a n increasing concentration of hydrogen sulphide. the plateau seems to be higher for the low temperatures. rather than on the absolute amount of H2S.e. Kinetic measurelnents were carried out with about 40% added H a .. the plateau occurs a t approxinlately the same relative rate in all cases. FIG. 1. and 530" C. i.201. Curve B is a similar tracing showing the decomposition of 85 mm of dimethyl ether .e. I. Relative rate (vluu) against pressure of hydrogen sulphide for three different pressures of ether: @ 100 mm.McKENNEY AND LAIDLER: DIMETHYL ETHER PYROLYSIS. Chem.nrcresearchpress. Hydrogen sulphide in the amount of 40% was sufficient to ensure "limiting" acceleration (independent of H2S).17 on 01/24/12 For personal use only. while over 75y0H2S ensured t h a t the reaction was in the region dependent on the percentage of hydrogen sulphide. the lower the ether pressure. This slight pressure change is insignificant compared to the pressure change for the decomposition of dimethyl ether in the presence of H2S. As still greater quantities of H2S are added the relative rate increases linearly. I t is apparent from the curves shown in Fig. Points were determined a t three different temperatures-480. Preliminary experiments were carried out with hydrogen sulphide alone in the reaction vessel a t GOO0 C. Within the experimental error. This suggests t h a t the eflects depend only on the proportion of H2S relative to ether. the rate in the presence of H2S divided by the rate in the absence of H2S) is shown in Fig. J. In order to verify the experimental results of previous workers (6) the rate of decotnposition of dimethyl ether was measured for various added amounts of hq-drogen sulphide. A 300 mm. A plot of relative rate against the percentage of hydrogen sulphide (Fig.

The slope of the line is 0. for the reaction in the plateau region where about 40% H2S was added.6 41. The lines all have slopes of 1.30 1 .2012 CANADIAN JOURXAL O F CHEMISTRY.7 28 2. Both runs were carried out a t 510° C.com by 112.2 2.6 2.4 2.3 2.8 2.e. Curve A is a tracing of the record obtained for the decomposition of 90 mm of ether in the absence of hydrogen sulphide.17 on 01/24/12 For personal use only.6 2. Downloaded from www. 3 1 1. in the presence of 475 mnl of H2S. 3.5.2 1 . 10.27 1. 4 1 .4 1. m J -0. LT -0.5 f P . Double logarithmic plot of inflection rate against ether pressure for various temperatures.4 Log 2. The accelerating effect of the added H2S is readily seen. These curves were determined for the decomposition in the presence of about 40% HBS(i.5. V O L .9 (rnrnl in the presence of about 40y0 HBS(i. FIG. the plateau region). 5.33 2. The ether pressure was coilstant a t about 20 mm.28 1. -1.25 1.nrcresearchpress.4 -1. 4.2 2.0 -1. The temperature in both cases was 510" C. 5.0 2.4 r0.5 -1. All of the lines have slopes of 1.5.29 1. 2 103 .2 -1.201.0 -0.32 1.24 1. 1963 +0. Arrhenius plot for the deco~nposition FIG. lmml FIG.27.5 -18 0 200 400 600 600 1000 1200 1. Typical pressure-time curves. The corresponding Arrhe~liuscurve is shown in Fig. Curve B is a similar tracing showing the decomposition of 85 mm of ether in the presence of 475 mm of H2S.4 :.26 1. J. FIG.2 0.6 -0.e.2 Can. 6 1. 6. Figure-4 shows plots of the logarithm of the rate against the logarithm of the ether pressure.1 2. Double logarithmic plot of inflection rate against pressure of hydrogen sulphide a t 520' C.8 TIME ( s e c l Log P . . Chem. the plateau region). 2.

The calculated activation energy for the reaction accelerated by very high percentages of hydrogen sulphide is 52. The kinetic measurements made with 75 to 99% H2S are shown in Figs. 111 2013 The three-halves-order rate constant may be expressed as k = 1. DISCUSSION The fact that the rate of decomposition of dimethyl ether in the presence of hydrogen sulphide relative to the rate in the absence of hydrogen sulphide depends on the proportion of H2Sto ether (see Figs.82X1016e-61~8001RT cc1I2m01e-~/~ sec-I obtained by Imai and Toyama (6). Arrhenius plot for the decomposition in the presence of 75-99% HZS.McKENNEY AND LAIDLER: DIMETHYL ETHER PYROLYSIS.5. Figure 6 is a double logarithmic plot of rate against pressure of hydrogen sulphide. 1 and 2) suggests that competitive reactions are involved in the process. 6. constant (-20 mm) pressure of dimethyl ether. At these temperatures it is well known that dimethyl ether decomposes to form methyl and methoxy radicals.06X1014e-53. 5 0 0 / R T cc1/2 mole-1/2 sec-l. showing that the order with respect to H2S pressure is one-half in the region of very high percentages of HZS. Downloaded from www.27. 8. This is suggested by the fact that there is a slight decrease in pressure when H2S alone is present in the reaction vessel a t 600' C. The corresponding Arrhenius plot is shown in Fig. These curves were determined for the decomposition in the presence of 7 5 9 9 % H2S.2001RT cc1I2 mole-lJ2 sec-l. and 8.98X1014 e-52 .nrcresearchpress. 7. Hydrosulphide radicals are almost certainly formed from the decomposition of hydrogen sulphide. T h e Iine drawn has a slope of 0. The lines all have slopes of 1. The logarithm of the rate minus one-half the logarithm of the hydrogen sulphide pressure is plotted against the logarithm of the ether pressure in Fig. The rate constant may be expressed by k = 4. J. Chem.8.7. The evidence suggests that the decomposition . A plot of this kind enabled the dependence on ether pressure t o be determined. All of the lines drawn in Fig. The thermal decomposition of hydrogen sulphide has in fact been studied in the temperature range employed in this research (9). FIG.5.com by 112.17 on 01/24/12 For personal use only. for a Can. without the tedious task of holding the H2S pressure constant.201. FIG. 7 have slopes of unity. Double logarithmic plot of inflection rate against ether pressure for various temperatures. This is to be compared with k = 1.5 kcal mole-'. 7.

i. there should be a plentiful supply of hydrosulphide radicals. n = 1/2 and m = 1.27. the second predicting dependence with respect t o both hydrogen sulphide and dimethyl ether. CHaOCH3 + HS --t H2S + CHaOCHz. J.201. 1963 proceeds mainly by heterogeneous processes a t temperatures below 600" C.17 on 01/24/12 For personal use only. Chem. and can also be produced from reactions such as CH3 + H2S --t CHa + HS. Figures 6. for the reaction with high percentages of H2S. The mechanism to which these considerations lead can be written as: . 7. 10) T h e shape of the curves shown in Figs.e. 1 and 2 suggests the following relationships: This reduces t o Thus on a plot of relative rate (v/vo) against the percentage of hydrogen sulphide a plateau would be observed when the proportion of H2S to CHBOCH? is small and k"jk is the dominant term. 41. as the ratio of H2S to CHBOCHB becomes larger the relative rate should then increase with increasing percentage of hydrogen sulphide.nrcresearchpress. The radical HS would probably be formed in large quantities.com by 112. These could initiate the ether decomposition by abstraction of a hydrogen atom. during the decomposition of dimethyl ether in the presence of hydrogen sulphide. However. and 8 show that the order is one-half in H2S and first in CHBOCHZ.2014 CANADIAN JOURNAL O F CHEMISTRY. The overall rate expression for the thermal decomposition of pure dimethyl ether is of the form (Part I and ref. Consequently. Downloaded from www. V O L . Can. The rate expression for the reaction in the presence of H2S should therefore involve two terms-one predicting three-halves-order behavior with respect t o dimethyl ether and no dependence on hydrogen sulphide.

Downloaded from www. ~ Z (2k19) O [CH~OCHZ] = . to describe the rate for thc plateau region the follou~ing expression can be written : This expression is identical with that postulated by Imai and Toyama (6). The ratio of the first to the second term is This expression becoines greater than unity when the ratio [H2S]/[CH30CH3]becomes greater than 9.--k~ k23a lt2 [CH3 0 ~ ~ 3 1 [H~s]~" + k3 (2k -A [CH k23a) 'I2 3 0 ~ ~ ~ 1 ~ ' ~ The rate is given by The first and fourth terms in this expression are small in comparisonTto the second and third terms. and k19 from Table I. The reason .nrcresearchpress. The agreement is therefore quite satisfactory in view of the uncertainties in the rate constants. I11 2015 where 14 represents a third body. Thus the first term in the rate expression predominates when the pressure of hydrogen sulphide exceeds 90%.201. Chem.17 on 01/24/12 For personal use only.com by 112. The rate-can therefore-be written as A crude estimate of the percentage of 1-12s a t which the change in order takes place can be made using the values for 81.27. The transition actually takes place with about 50-7070 H2S. Consequently. J. and hence may be neglected.1.hlcKESKEY AKD LAIDLER: DIMETHYL ETHER PYROLYSIS. Application of the conventional steady-state approximation yields for the radical concentrations: Can.

Downloaded from www. In the region of high percentages of H2S the rate is given by Experimentally the reaction is one-half order with respect to hydrogen sulphide and first order with respect to dimethyl ether in this region. and hence [24] can be ignored. the equilibrium process + + + + has been included in the mechanism. NOTE:T h e values for reactions [I91 and [23a] were calculated in the same manner as in the Appendix of Part I.5 kcal mole-'. V O L . In view of this evidence. Thus with the neglect of reactions [I91 and [5].com by 112. taken for M + + + for this is that reaction [19] is unimportant until large relative quantities of hydrogen sulphide are used. in agreement with experiment. in good agreement with the experimental value of 53. that about 13% of the HS radicals disappeared by the reaction 2HS -+ Sz H z while about 87% reacted by the process 2HS --+ H2S S followed by 2 s M -+Sz M. cc mole-' sec-l.17 on 01/24/12 For personal use only.8 kcal mole-l. The reaction in this region is therefore predicted t o be three-halves order with respect to ether. The predicted activation energy is given by E = E20+3(Ela-EZ3&). Four effective SH.E = z 56.0X1014 cc1I2 sec-'. or cc2 mole@ sec-') Reference See Part I Estimated (see footnote) Assumed See Part I Imai and Toyama (11) Estimated (see footnote) See Part I See Part I Can. Chem. cc mole-I sec-I. 1963 TABLE I Kinetic parameters Frequency factor (sec-I. The predicted frequency factor is A = Azo(2A19/A23a)112 = l. whereas the experimental value is A = 4.M. by analogy with hydrogen peroxide. . The predicted activation energy is E = E ~ o + $ ( E ~ ~ .2016 CANADIAN JOURNAL O F CHEMISTRY.2 kcal mole-l. from a study the photolysis of H2S. in agreement with this rate expression. The predicted frequency factor is A = A20(2A1a/A23a)1/2 = 1.nrcresearchpress. The small quantity of S atoms produced may react with H2S a s shown or with CH3OCH3: I t is suggested that reaction [-221 is faster than [24].98 X 1014CC'/~ mole-112 sec-l. the mechanism is essentially the same as that postulated by Imai and Toyama (6). or cc2 set-I) Activation energy (kcal mole-') Reaction k a t 800" K (sec-'. This is also in good agreem e n t with the experimental value of 1.201.27.3 ~ ~ ) kcal mole-l. The Termination Reaction Darwent and Roberts (9) concluded. J. Substitution of the appropriate values given in Table I yields E = 52.06X 1014cc1I2mole-'I2 sec-'. in fair agreement with the experimental value of 52. 41.0 X lo1*cc1I2 sec-l. and three effective degrees of freedom were degrees of freedom were assumed for HS H2S + H HS 4.

9 kcal mole-l. This yields D(H-SH) = 92 kcal mole-'.65 kcal mole. This observation is important with reference to the mechanism of the uninhibited reaction.7 kcal mole-'. H.7 by mass spectrometric techniques. The Initiation Reaction An important conclusion arises from this study with regard to the order of the initiation reaction: the dissociation of the ether molecule into the radicals CH3 and CH30. and H2S are known (14). This value yields D(H-SH) = 84. The experimental difference is 0. J. Since El.nrcresearchpress. in good agreement with our value. as discussed in Part I. Consideration of the steady-state equations shows that the only apparent way t o obtain the correct pressure dependence in both H2Sand CH3OCH3 is by having the initiation in its low-pressure second-order region. Cottrell (12) favors a more recent value of 57 kcal mole-' for AHfO(S). since the heats of formation of S.com by 112.2 kcal mole-' for AHfO(HS). 111 2017 The concentration of HS radicals is large in this system and their combination will give rise to H2S2.17 on 01/24/12 For personal use only.27. Downloaded from www.9 kcal mole-'. Mackle and McClean (16) prefer a value of 35. Johns and Ramsay (13) recently determined the dissociation energy of the hydrosulphide radical and obtained D(H-S) = 81. This can be used t o calculate a value for D(H-SH). E19= El. + SH = 80. Chem.201.9 kcal mole-'. and Ansdell and Page (15) support this value on the basis of their determination of the electron affinity of the sulphur atom.-2AE = E l 9 can be 85. which was determined from a calorimetric study of benzyl mercaptan.6 kcal mole-'. On the other hand. Palmer and Lossing (17) recently determined AHfO(HS) < 33. + D(S-H) = AHlO(S)+AHP(H) --AHrO(SH) whence AHfo(SH) For H2S -+ H = 23. values varying from 81 to 95 kcal mole-' have been reported (12). a t high pressures.McKENNEY AND LAIDLER: DIMETHYL ETHER PYROLYSIS. is known (Part I) calculated as. The difference between the activation energies for the reaction in the plateau region and the region of high H2S percentages is given from the overall rate expression as Can. Previous work has led to conflicting values for this dissociation energy. and this leads to an estimate . The Dissociation Energy of Hydrogen Sulphide The present work provides a method of estimating the dissociation energy (D(H-SH)) of hydrogen sulphide. For the process SH -+ S H.4~t2. This reaction will require a third body under these experimental conditions.

6 kcal mole-l was taken for the calculations considered above. This explains why the relative rate seems to increase with decreasing temperature.7 kcal mole-l.45 kcal mole-l. 53.201.27. + CH30CH3 -+ CH3 + CH3OCH3 M CH3OCHZ + + M + CH3O + CHaOCH.com by 112. H -+ -t + CH3O + &/I CH4 + CH3OCHZ CHZO + CH3 CH20 + H + M Hz + CHZOCHZ CzH6 + M. Similarly for the region using high percentages of hydrogen sulphide the relative rate is given by .nrcresearchpress. Chem.e. The value of 85. J.17 on 01/24/12 For personal use only. i.< 90.2-54. 41. The fact that -1.7 is so small is indicated from Fig. 1963 of D(H-SH) . Admittedly the experimental errors involved in this estimation are large.9 = -1.for the reaction in the presence of 40y0 HpS. [la] [2I [31 141 El [71 T h e overall rate expression derived by means of the usual steady-state approximation is given by I t was shown above that the rate expression for the reaction in the plateau region (-30 to 50y0 added HpS) can be written as The relative rate is therefore which reduces to The predicted activation energy for the relative rate in this region is therefore E = E~o-Ez+$(E~-Ez~~). The value is therefore still in doubt. The Efect of Temperature on the Relative Rate The main features of the thermal decomposition of dimethyl ether can be represented by the following scheme (see Part I ) : Can.2018 CANADIAN JOURNAL O F CHEMISTRY. M + CH. + CH. 2. CH. which shows that the curves for the three temperatures fall very close to one another. but our value of 85. This is in good agreement with the experimental value determined by subtracting the activation energy for the reaction in the absence of H2S from the activation energ).6 kcal mole-l.6 kcal mole-' calculated from the difference in activation energies supports the lower values. Substitution of the appropriate values from Table I yields E = -0. Downloaded from www. VOL.

Japan. F . T h e authors are indebted to Dr. Std. DE B. 17. COTTRELL. MACKLE and R. h-.o-E2+~(E. (London).4 kcal mole-l. 895 (1962). Bull. REFERENCES 1. 221 (1953). 2807 (1957). 1008 (1959).) 3. Proc. Ser. KERRand A. TOYAAIA. N. WOJCIECHOWSKI. F. Chem.. Butter\vorths Scientific Publications. and 0. 13. K. Bur. 11. 4. Chem.-DICKEKSOX.201. A. E. 1%'. 1084 (1962). H. LAIDLER and B. 14. 34. I11 The activation energy for the relative rate is predicted to be E = E. WATERS. Soc. 35.-E23. 216. MCCLEAN. PAGE. Soc. Sac. Japan. BIKKELL. Soc. Y. (U. JAIX. J. IMAIand 0. Bull. Trans. RAMSAY. TOYAMA. 14: 15. F. IMAIand 0. J. Chem. 9. J. Phys. ROBERTS. TOYAMA. -q. Discussions Faraday Soc. TROTMA~. ' J . Can. Proc. A. 1408 (1960). J . 4661 (1962). 500. 3322 (1957). B. Chem. 8. D. 16. ~VILKIE. 652 (1960). TOYAMA. J. 84. K. BENSON and D. 33. Chem. P. London.McKENXEY AND LAIDLER: DIMETHI'L ETHER PYROLYSIS. (London). PALnfER-and F.85 kcal mole-l. 33. and H. A. TROTMAN-DICKENSON. Japan. B. 344 (1953). 58. J . Soc. = This is in fair agreement with the experimental value of -2. Soc. Faraday Soc. 1958. 1120 (1960). T . IMAIand 0. W. Ser. The strengths of chemical bonds. A. Phys. TOYAMA. YOSHIDA.J. A. V. R.Bull. Bull. 328 (1961). W. Roy. Bull. p. 391 210(1961). 58. considering the uncertainties in the individual activation energies. Am.ANSDELL and F. C. 3. Chem. 5. Faraday Soc. N. 31. BARRETT and W. . SMITH. C h e n ~ Soc. . S. R. DARWEKT S. LOSSING. Soc.com by 112. F. N. M. Soc. Chem. 7. 1952. T.+E7-E1. Japan. 257 (1960). 752. JOHXS SELECTED VALUESOF CHEMICAL THER~IODYNA~IIC PROPERTIES. Roy. N. J. Chem. Trans. Chem. 188.IVAI and 0. Soc. B. N. A.nrcresearchpress. 259. ACKNOWLEDGMEXTS Can.). 759 (1962). Circr. and D .S. and R. W. 2. The work was supported by grants from the National Research Council and the Petroleum Research Fund. Wojciechowski for valuable suggestions. L. 6. IMAI.27.17 on 01/24/12 For personal use only. Japan. Downloaded from www. 33. J. 12. Natl. 10.

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