Thermal stability of primary amines

Tsang, Wing

doi:10.1002/kin.550100105

Cited by 31 publications

(27 citation statements)

References 21 publications

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“…Recent evaluations by Tsang [16] yield higher values for CzHr than the one used here. A major conclusion of our results is that a relatively "high" value of AHy(i-C6H1r) is obtained even if the "low" value of AHF(C2Hy) is used.…”

Section: Discussionmentioning

confidence: 51%

The azoethane‐initiated thermal reaction of isobutene. Heat of formation of the 2‐methyl‐2‐pentyl radical

Serés¹,

Görgényi²,

Farkaš³

1983

Int J of Chemical Kinetics

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The azoethane-sensitized thermal reaction of isobutene has been studied at 526-565 K.The initial concentrations of azoethane and isobutene were in the ranges of 1.40-10.5 X and 6.78-26.6 X mol/dm3, respectively. From the initial rates of formation of ethane and 2-methylpentane the heat of formation of the 2-methyl-2-pentyl radical was determined. The result obtained is q(2-methyl-2-pentyl) = 0.8 f 2.0 kcal/mol. The entropy of the radical, obtained from statistical mechanical calculations and experimentally, is S0(2-methyl-2-pentyl) = 92.8 f 1.5 cal/mol-K. The results support the high heat of formation of the t -butyl radical suggested by different authors.

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Section: Discussionmentioning

confidence: 51%

The azoethane‐initiated thermal reaction of isobutene. Heat of formation of the 2‐methyl‐2‐pentyl radical

Serés¹,

Görgényi²,

Farkaš³

1983

Int J of Chemical Kinetics

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“…6 We then obtain AH;(t-butyl, 300 K) = 9.5 f 0.8 where the error limits have been estimated from assumed error limits of f0.2 in log (K2).…”

Section: Tmb 2t-c4hgmentioning

confidence: 99%

The rate constant for t‐C₄H₉ → H + i‐C₄H₈ and the thermodynamic parameters of t‐C₄H₉

Canosa

Marshall

1981

Int J of Chemical Kinetics

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T h e rate of the reverse reaction of the system (1,-1) H + i-CdH8 72 t-CdH, has been measured in the range of 584-604 K from a study of the azomethane sensitized pyrolysis of isobutane. Assuming the published value for the rate constant of recombination of t -butyl we obtain log k-l(sec-') = 14.67 -39.4 kcal/mol/(2.3RT) Combination with our published data for k l permits the evaluation log K1 (atm-I) = 7.94 a t 600 K We have modified a previously published structural model of t-butyl by the inclusion of a barrier to free rotation of the methyl groups in order to calculate values of the entropy and enthalpy of t-butyl a s a function of temperature. Using standard data for H and for i-C4Ha we obtain AH;(t-butyl, 300 K)(kcal/mol) = 10.6 f 0.5We have obtained other, independent values of this quantity by a reworking of published data using our new calculations of the entropy and enthalpy o f t -hutyl. There is substantial agreement between the different values with one exception, namely, that derived from puhlished data on the equilibrium i-C4H10 + I = t-CdH9 + HI which is significantly lower than the other values.We conclude that the value AH/(t-butyl, 300 K)(kcal/mol) = 10.5 f 1.0obtained from the present work and a reworking of published data which involves the use of experimental data on t-butyl recombination is incompatible with the result based on itdination data.

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“…(5) and 897K. The five highest temperature points were obtained from experiments in shock tubes (14,15,18,19), for which temperatures are difficult to calculate and for which adjustments of k to k, are greater. For these reasons, data from shock tube experiments at even higher temperatures have been omitted.…”

Section: Discussionmentioning

confidence: 99%

“…In the studies of (3,4). It has now been the subject of at least 20 the collision efficiency at high temperatures (16,18, experimental studies (1,2,(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22) and at least three 20, 221, km was calculated starting with the above RRKM models (3,4, 23).…”

Section: Introductionmentioning

confidence: 99%

The pressure dependence of the rate of isomerization of cyclopropane at 897 K

Furue¹,

Pacey²

1982

Can. J. Chem.

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HIROSHI FURUE and PHILIP D. PACEY. Can. J. Chem. 60,916 (1982). The isomerization of cyclopropane has been studied in a flow reactor at 897 K and from 4 to 406 Tom. The pressure dependence of the rate constants from this work and from the literature have been compared with predictions obtained from two models based on the theory of Yau and Pritchard and from three RRKM models. The collisional deactivation efficiency was found to generally decline with increasing temperature. The average energy removed per collision was calculated by the method of Tardy and Rabinovitch and was found to have values from 15 to 23 kJ mol-I at 897 K. Combining the results of this work with data from the literature from 690 to 1038 K, the limiting high pressure rate constants follow the relation log k , = 15.50 k 0.14 -(276.0 k 2.1 kJ mol-')/2.3RT. HIROSHI FURUE Introductionselves, reliable, limiting high pressure values, k,, The isomerization of cyclopropane has played an based on extrapolation of data from a number of important part in the study of unimolecular reac-Pressures, have been obtained between 718 K and tions. Because it is a reasonably clean reaction 773K 2, 59 7). There have been six recent system, it was the subject of early, successful studies of the pressure dependence of the rate at experimental investigations (l,2). In turn, because higher temperatures (17-221, but the pressure of the availability of the experimental data, it was ranges were narrow and the authors did not extrapone of the first reactions used to test RRKM theory olate their data to determine k,. In the studies of (3, 4). It has now been the subject of at least 20 the collision efficiency at high temperatures (16, 18, experimental studies (1, 2, 5-22) and at least three 20, 221, km was calculated starting with the above RRKM models (3,4, 23).Arrhenius parameters determined at lower temperDespite this impressive body of work, some atures. Even these relatively precise Arrhenius questions remain. RRKM models which were de-Parameters can lead to an uncertainty in k, at veloped to reproduce the fall-off of the rate con-1mOK of50%-stant at low pressures at one temperature haveThe Purpose of the Present work is to study the been found to be unsuccessful at other tempera-reaction at high Pressures and high temperatures tures (4). It has been suggested (16,17) that this is using a flow system. Such a system can provide caused by a decline in P, the efficiency of collisions activation energies (24) and reaction orders (251, in removing excess vibrational energy, as the d 1n kld In P , with a precision of 2 or 3%. This temperature increases. The evidence for this is precision is not better than that of the activation strong for collisions of cyclopropane with small energy quoted above, soexperiments were restrict-

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Thermal stability of primary amines

Cited by 31 publications

References 21 publications

The azoethane‐initiated thermal reaction of isobutene. Heat of formation of the 2‐methyl‐2‐pentyl radical

The azoethane‐initiated thermal reaction of isobutene. Heat of formation of the 2‐methyl‐2‐pentyl radical

The rate constant for t‐C₄H₉ → H + i‐C₄H₈ and the thermodynamic parameters of t‐C₄H₉

The pressure dependence of the rate of isomerization of cyclopropane at 897 K

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Thermal stability of primary amines

Cited by 31 publications

References 21 publications

The azoethane‐initiated thermal reaction of isobutene. Heat of formation of the 2‐methyl‐2‐pentyl radical

The azoethane‐initiated thermal reaction of isobutene. Heat of formation of the 2‐methyl‐2‐pentyl radical

The rate constant for t‐C4H9 → H + i‐C4H8 and the thermodynamic parameters of t‐C4H9

The pressure dependence of the rate of isomerization of cyclopropane at 897 K

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The rate constant for t‐C₄H₉ → H + i‐C₄H₈ and the thermodynamic parameters of t‐C₄H₉