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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:
HCOOH → CO2 + 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 |