EFFECT OF TEMPERATURE, SURFACE AND DIVERS REAGENTS ON THE KINETICS OF THE VAPOR PHASE REACTION, 2NO SUB 2 PLUS ROH GOING TO AND GOING FROM HNO SUB 3 PLUS RONO AT LOW PRESSURE
Abstract
The reaction was investigated in a bath system at partial pressures up to 10 mm Hg for all components employed. The rates were followed photometrically, and the NO2 concentrations were determined as a function of time. The addition of NO, diverse nitrite esters, and acetaldehyde did not affect the initial rate of the reaction, but NO entered the later stages of the reaction by reacting with the HNO3 which was produced in the primary reaction. When 0.5 mm of HNO3 which was produced in the primary reaction. When 0.5 mm of HNO3 vapor was added in the feed charge, the initial rate constant changed from 0.028 to 0.038. The temperature effects were determined in an apparatus which had a smaller surface volume ratio (S/V) than a previously used apparatus. The reaction rate depended on the second power of NO2 partial pressure but on less than the first power of the alcohol pressure. As the temperature varied from 0 to 75 C, the order of the reaction with respect to the alcohol changed from 0.3 to 0.8. The reaction rates at comparable temperatures were greater at higher S/V ratios than at lower ones. Different rate effects were observed when alcohol or NO2 was admitted first to the reaction cell. The higher S/V ratios indicated an average equilibrium constant (K) 0.97/mm at 25 C. hr for EtOH was determined by plotting log K vs 1/T hr for the reaction 2NO2 + standard molal entropy of EtNO2 was 84 cal/deg mol. The results are discussed and compared with previous findings, and the quantiative data are presented graphically.
Document Details
- Document Type
- Technical Report
- Publication Date
- Jul 01, 1953
- Accession Number
- AD0017683
Entities
Organizations
- University of Notre Dame