Kinetics of the water gas shift reaction catalyzed by rhodium(III) chloride in aqueous picoline studied by use of a continuous-flow stirred reactor

• Published in: Inorganic chemistry 1991-10, Vol.30 (20), p.3837-3842
• Main Authors: Lima Neto, Benedito S, Ford, Katherine Howland, Pardey, Alvaro J, Rinker, Robert G, Ford, Peter C
• Format: Article
• Language: English
• Subjects: 01 COAL, LIGNITE, AND PEAT; 010408 - Coal, Lignite, & Peat- C1 Processes- (1987-); 10 SYNTHETIC FUELS; 100200 - Synthetic Fuels- Production- (1990-); 400201 - Chemical & Physicochemical Properties; AZINES; CARBON COMPOUNDS; CARBON MONOXIDE; CARBON OXIDES; CATALYSIS; CATALYSTS; CATALYTIC EFFECTS; CHALCOGENIDES; CHEMICAL REACTION KINETICS; CHEMICAL REACTIONS; CHEMICAL REACTORS; Chemistry; CHLORIDES; CHLORINE COMPOUNDS; DATA; Exact sciences and technology; EXPERIMENTAL DATA; HALIDES; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; HOMOGENEOUS CATALYSIS; HYDROGEN COMPOUNDS; INFORMATION; Inorganic chemistry and origins of life; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; KINETICS; Kinetics and mechanism of reactions; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; PICOLINES; PYRIDINES; REACTION KINETICS; REFRACTORY METAL COMPOUNDS; RHODIUM CHLORIDES; RHODIUM COMPOUNDS; TRANSITION ELEMENT COMPOUNDS; WATER; WATER GAS PROCESSES
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic00020a013

Described is a kinetics investigation of the homogeneous water gas shift catalysis by rhodium(III) chloride in aqueous picoline solution. These investigations were carried out under flow conditions using a continuous-flow stirred reactor, which allowed the systematic variation of the reaction conditions (P[sub CO], T, flow rate, P[sub tot], [Rh][sub tot]). The catalysis rates proved to be nonlinear in [Rh][sub tot] over the range 3-20 mM, a result which was interpreted in terms of the system having dinuclear and mononuclear rhodium species present, both types of species being catalytically active but the mononuclear cycles being the more reactive. The rates also displayed a nonlinear dependence on P[sub CO] over the range 0.3-1.8 atm, although this was independent of [Rh]. The kinetics behavior with respect to P[sub CO] leads to the proposal of the reversible addition of CO to the catalytically active species prior tothe rate-limiting step in both the mono- and dinuclear catalytic cycles.