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Author(s):   Saito, K.; Shiose, T.; Takahashi, O.; Hidaka, Y.; Aiba, F.; Tabayashi, F.
Title:   Unimolecular decomposition of formic acid in the gas phase - On the ratio of the competing reaction channels
Journal:   J. Phys. Chem. A
Volume:   109
Page(s):   5352 - 5357
Year:   2005
Reference type:   Journal article
Squib:   2005SAI/SHI5352-5357

Reaction:   HCOOHCO2 + H2
Reaction order:   1
Temperature:   1350 - 1700 K
Pressure:  3.79E13 bar
Rate expression:   1.6x108 [s-1] e-181167 [J/mole]/RT
Category:  Experiment
Data type:   Absolute value measured directly
Pressure dependence:   Rate constant is pressure dependent
Experimental procedure:   Shock tube
Excitation technique:   Thermal
Time resolution:   In both real time and by end product analysis
Analytical technique:   Other (IR)
Comments:   Formic acid was produced via thermal (shock induced) dissociation of the dimer. Reaction of the monomer was followed by monitoring CO formation in real time via IR emission at 4.63 um and CO2 formation at 4.23 um. CO2 formation was more difficult to follow as it was produced in only about 2 to 8% of the CO. CO, CO2, and H2 products were also determined via GC analysis.

The precise temperature range is not reported in the paper. The listed values are approximate and were derived from the Arrhenius plots given in Figure 4 of the paper.

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Rate constant values calculated from the Arrhenius expression:

T (K)k(T) [s-1]
1350 1.56E1
1375 2.10E1
1400 2.79E1
1425 3.66E1
1450 4.76E1
1475 6.14E1
1500 7.86E1
1525 9.97E1
1550 1.26E2
1575 1.57E2
1600 1.95E2
1625 2.40E2
1650 2.94E2
1675 3.59E2
1700 4.34E2