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Research Papers: Evaporation, Boiling, and Condensation

# High Temperature Thermal Decomposition of Diethyl Carbonate by Pool Film Boiling

[+] Author and Article Information
C. Thomas Avedisian

Sibley School of Mechanical
and Aerospace Engineering,
Cornell University,
Ithaca, NY 14853-7501
e-mail: cta2@cornell.edu

Wei-Chih Kuo

Sibley School of Mechanical
and Aerospace Engineering,
Cornell University,
Ithaca, NY 14853-7501
e-mail: wk253@cornell.edu

Wing Tsang

Physical and Chemical Properties Division,
National Institute of Standards and Technology,
Gaithersburg, MD 20899
e-mail: wingtsang2000@yahoo.com

Sibley School of Mechanical
and Aerospace Engineering,
Cornell University,
Ithaca, NY 14853-7501
e-mail: al659@cornell.edu

1Corresponding author.

2Present address: CGG, 10300 Town Park Drive, Houston, TX 77072.

3Present address: Department of Mechanical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, VA 24061.

Contributed by the Heat Transfer Division of ASME for publication in the JOURNAL OF HEAT TRANSFER. Manuscript received March 15, 2017; final manuscript received September 19, 2017; published online February 27, 2018. Editor: Portonovo S. Ayyaswamy.This work is in part a work of the U.S. Government. ASME disclaims all interest in the U.S. Government's contributions.

J. Heat Transfer 140(6), 061501 (Feb 27, 2018) (10 pages) Paper No: HT-17-1145; doi: 10.1115/1.4038572 History: Received March 15, 2017; Revised September 19, 2017

## Abstract

We use the configuration of film boiling on a horizontal tube positioned in a stagnant pool of saturated diethyl carbonate (DEC, $(C2H5O)2CO$) to study DEC decomposition at temperatures up to 1500 K. The composition of bubbles that percolate through the liquid pool is measured and the results are used to infer the decomposition reactions. The results show that below tube temperatures of about 1100 K, the decomposition products are ethylene (C2H4), carbon dioxide (CO2), and ethanol (EtOH, C2H5OH) with a molar ratio nC2H4/nCO2∼1, which is consistent with a first-order decomposition process. At higher temperatures, nC2H4/nCO2 > 1 which is explained by an additional route to forming C2H4 from radicals in the system (created by EtOH decomposition) attacking DEC. The presence of H2, CO, CH4, and C2H6 in the product stream was noted at all temperatures examined with concentrations that increased from trace values at low temperatures to values comparable to the DEC unimolecular process at the highest temperatures. Formation of a carbon layer on the tube was observed but did not appear to influence the decomposition process. A scale analysis shows that the rate constant controls decomposition compared to the residence time, which has a weaker dependence on temperature.

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## Figures

Fig. 1

Schematic of film boiling on a horizontal tube of outside diameter Do. The gas flow in the vapor film (the “reactor”) is driven by buoyancy and the gases decompose during their transport. Departing bubbles contain decomposition products along with unreacted DEC. This schematic view corresponds to section a–a of the inset photograph in Fig. 4.

Fig. 2

Schematic of the apparatus

Fig. 3

Calibration of Inconel 600 electrical resistivity with temperature. Data are from Ref. [35] up to 1200 K. Curve-fit is linear, ρ(μΩ − m) = 0.99027 + 1.4266 × 10−4T (K). Dotted line is extrapolation of linear fit above 1200 K.

Fig. 4

Variation of heat flux with average tube temperature for DEC. Symbols in the film boiling regime come from a quadratic fit to the heat flux data while the bars indicate standard deviations of the fluxes around the data. The upper temperature is determined by the thermal integrity of the tube material and the lower temperature (as measured in the experiments) corresponds to the onset of destabilization of the film initiated by liquid/solid contacts. The inset is a photograph showing the film boiling configuration at a tube temperature of 868 K. A schematic of section a–a is shown in Fig. 1.

Fig. 5

Variation of total volumetric flux of exhaust gases with temperature. Reaction rate is low below about 700 K, which also coincides with destabilization of the vapor film.

Fig. 6

Volumetric fluxes of noncondensable products in exhaust gas. CO2 and C2H4 are products of DEC decomposition (Eq. (1)). The other species are speculated to form from EtOH decomposition due to radical reactions.

Fig. 9

Schematic of temperature variation across δ. Tt is a threshold temperature defined by ε (Eq. (A2)) and δt is the corresponding reaction boundary layer that supplies product gases from decomposition. The product species are formed mainly over y < δt/δ at an average temperature within this layer while the remaining supply of product gases comes from δt/δ < y < 1.

Fig. 8

(a) EDX analysis of a carbon flake with insert SEM image and (b) EDX analysis of a bare tube with SEM image shown in inset

Fig. 7

Variation of [C2H4]/[CO2] (data from Fig. 7) with tube temperature (K)

Fig. 10

(a) Variation of ε across the vapor film for Eq. (1) corresponding to the indicated Tw and (b) variation of ΔT = Tw − Tmr with ε. Inset expands the scale around ε = 1.

Fig. 11

Schematic of vapor film showing the coordinates for scale analysis to determine the buoyant gas velocity (VB), residence time (tr), and vapor film thickness (δ). δ is shown as nearly constant though in reality it varies with θ.

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