Two experiments for the introductory chemical reaction engineering course

This paper describes a pair of chemical reaction experiments developed for Rowan University's introductory course in chemical reaction engineering: an esterification reaction carried out in a packed bed, and a competitive reaction in which the kinetics were influenced by micromixing.

The first experiment is the esterification of ethanol and acetic acid to form ethyl acetate. Students first examine this reaction in their organic chemistry class. The experiment developed in this project re-examines this reaction from a chemical engineering perspective. For example, the reaction is reversible and equilibrium-limited, but in the organic chemistry lab, there is no examination of the kinetics. The complementary chemical engineering experiment examines the relationship between residence time and conversion.

The second experiment is a competitive system involving two reactions:

H₂BO₃⁻ + H⁺ ↔ H₃BO₃

5I⁻ + IO₃⁻ + 6H⁺ → 3I₂ + 3H₂O

The first reaction is essentially instantaneous. Thus, when H⁺ is added as the limiting reagent, a perfectly mixed system would produce essentially no I₂. Production of a significant quantity of I₂ is attributed to a local excess of H⁺; a condition in which all H₂BO₃⁻ in a region is consumed and H⁺ remains to react with I⁻ and IO₃⁻.

In the spring of 2005, for the first time, both experiments were integrated into the undergraduate chemical reaction engineering course. This paper describes the use of the experiments in the classroom and compares the performance of the 2005 students to the 2004 cohort, for whom the course included no wet labs at all.     

The Identification of 2,4-diacetylphloroglucinol as an Antifungal Metabolite Produced by Cutaneous Bacteria of the Salamander <Emphasis Type="Italic">Plethodon cinereus</Emphasis>

Beneficial bacteria that live on salamander skins have the ability to inhibit pathogenic fungi. Our study aimed to identify the specific chemical agent(s) of this process and asked if any of the antifungal compounds known to operate in analogous plant–bacteria–fungi systems were present. Crude extracts of bacteria isolated from salamander skin were exposed to HPLC, UV-Vis, GC-MS, and HR-MS analyses. These investigations show that 2,4-diacetylphloroglucinol is produced by the bacteria isolate Lysobacter gummosus (AB161361), which was found on the red-backed salamander, Plethodon cinereus. Furthermore, exposure of the amphibian fungal pathogen, Batrachochytrium dendrobatidis (isolate JEL 215), to different concentrations of 2,4-diacetylphloroglucinol resulted in an IC₅₀ value of 8.73 μM, comparable to crude extract concentrations. This study is the first to show that an epibiotic bacterium on an amphibian species produces a chemical that inhibits pathogenic fungi.     

Microkinetic model for the pyrolysis of methyl esters: From model compound to industrial biodiesel

A tool for the generation of decomposition schemes of large molecules has been developed. These decomposition schemes contain radicals which can be eliminated from the model equations if both the μ‐hypothesis and the pseudosteady‐state approximation are valid. The reaction rate coefficients and thermodynamic parameters have been calculated by incorporating a comprehensive group additive framework. A microkinetic model for the pyrolysis of methyl esters with a carbon number of up to 19 has been generated using this tool. It is validated by comparing calculated and experimental yields of the pyrolysis of methyl decanoate and novel rapeseed methyl ester pyrolysis data in the temperature range from 800 to 1100 K and methyl ester partial pressure range from 1 × 10^?3 to 1 × 10^?2 MPa. This modeling frame work allows to not only assess the use of methyl ester mixtures as potential feedstock for olefin production but also their effect as blend‐in or trace impurity. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4309–4322, 2015     

Reversible Cluster Aggregation and Growth Model for Graphene Suspensions

We present a reversible cluster aggregation model for 2‐D macromolecules represented by line segments in 2‐D; and, we use it to describe the aggregation process of functionalized graphene particles in an aqueous SDS surfactant solution. The model produces clusters with similar sizes and structures as a function of SDS concentration in agreement with experiments and predicts the existence of a critical surfactant concentration (C_crit) beyond which thermodynamically stable graphene suspensions form. Around C_crit, particles form dense clusters rapidly and sediment. At C ? C_crit, a contiguous ramified network of graphene gel forms which also densifies, but at a slower rate, and sediments with time. The deaggregation–reaggregation mechanism of our model captures the restructuring of the large aggregates towards a graphite‐like structure for the low SDS concentrations. © 2017 American Institute of Chemical Engineers AIChE J, 63: 5462–5473, 2017     

Precursor gas chemistry determines the crystallinity of carbon nanotubes synthesized at low temperature

Despite significant progress in carbon nanotube (CNT) synthesis by thermal chemical vapor deposition (CVD), the factors determining the structure of the resulting carbon filaments and other graphitic nanocarbons are not well understood. Here, we demonstrate that gas chemistry influences the crystal structure of carbon filaments grown at low temperatures (500 °C). Using thermal CVD, we decoupled the thermal treatment of the gaseous precursors (C₂H₄/H₂/Ar) and the substrate-supported catalyst. Varying the preheating temperature of the feedstock gas, we observed a striking transition between amorphous carbon nanofibers (CNFs) and crystalline CNTs. These results were confirmed using both a hot-wall CVD system and a cold-wall CVD reactor. Analysis of the exhaust gases (by ex situ gas chromatography) showed increasing concentrations of specific volatile organic compounds (VOCs) and polycyclic aromatic hydrocarbons (PAHs) that correlated with the structural transition observed (characterized using high-resolution transmission electron microscopy). This suggests that the crystallinity of carbon filaments may be controlled by the presence of specific gas phase precursor molecules (e.g., VOCs and PAHs). Thus, direct delivery of these molecules in the CVD process may enable selective CNF or CNT formation at low substrate temperatures. The inherent scalability of this approach could impact many promising applications, especially in the electronics industry.     

Arsenic species in an arsenic hyperaccumulating fern, Pityrogramma calomelanos: a potential phytoremediator of arsenic-contaminated soils

The fern Pityrogramma calomelanos is a hyperaccumulator of arsenic that grows readily on arsenic-contaminated soils in the Ron Phibun district of southern Thailand. P. calomelanos accumulates arsenic mostly in the fronds (up to 8350 microg As g(-1) dry mass) while the rhizoids contain the lowest concentrations of arsenic (88-310 microg As g(-1) dry mass). The arsenic species in aqueous extracts of the fern and soil were determined by high performance liquid chromatography coupled to an inductively coupled plasma mass spectrometer (HPLC-ICPMS) which served as an arsenic specific detector. Only a small part of the arsenic (6.1-12%) in soil was extracted into water, and most of this arsenic (> 97%) was present as arsenate. The arsenic in the fern rhizoids was approximately 60% water-extractable, 95% of which was present as arsenate. In contrast, arsenic in the fern fronds was readily extracted into water (86-93%) and was present mainly as arsenite (60-72%) with the remainder being arsenate. Methylarsonate and dimethylarsinate were detected as trace constituents in only two fern samples. Preliminary estimates of phytoremediation potential suggest that P. calomelanos might remove approximately 2% of the soil arsenic load per year. With due consideration to the type of arsenic compounds present in the fern, and their water-solubility, the option of disposing high arsenic ferns at sea is raised for discussion.     

Organic nitrogen transformations in a 4-stage Bardenpho nitrogen removal plant and bioavailability/biodegradability of effluent DON

Nitrogen species, specifically, the fate and occurrence of organic nitrogen (ON) within a 4-stage Bardenpho process bioreactor producing low total nitrogen (TN) effluents were investigated in this study. The results showed release of ON in primary anoxic zone and no ON release in the first aerobic zone of the process. The research included investigation of biodegradability/bioavailability of wastewater-derived effluent dissolved ON (DON). The final-effluent DON utilization was evaluated by two different bioassay protocols in the presence and absence of nitrate. About 28–57% of the effluent DON was bioavailable/biodegradable. Bioavailable (to algae and bacteria) DON (ABDON) and biodegradable (to bacteria) DON (BDON) results did not show significant differences in terms of quantity, but DON utilization rates by ABDON (0.13 day⁻¹) protocol were higher than that of the BDON (0.04 day⁻¹) protocol in the nitrate-removal samples. As a result, ABDON requires a shorter time to exert the bioavailable fraction due to symbiotic relationship between algae and bacteria. In the nitrate-containing samples, it appears that nitrate competes with labile DON as a nitrogen source to microorganisms in both ABDON and BDON protocols. The first order decay rate of DON in the presence of nitrate was 0.11 day⁻¹ and 0.02 day⁻¹ for ABDON and BDON, respectively.