Continuous-flow Measurements

There are many potential advantages to kinetic methods of analysis, perhaps the most important of which is the ability to use chemical reactions that are slow to reach equilibrium. In this chapter we examine three techniques that rely on measurements made while the analytical system is under kinetic rather than thermodynamic control chemical kinetic techniques, in which the rate of a chemical reaction is measured radiochemical techniques, in which a radioactive element s rate of nuclear decay is measured and flow injection analysis, in which the analyte is injected into a continuously flowing carrier stream, where its mixing and reaction with reagents in the stream are controlled by the kinetic processes of convection and diffusion. 

By passing a continuous flow of solvent (admixed with a matrix material) from an LC column to a target area on the end of a probe tip and then bombarding the target with fast atoms or ions, secondary positive or negative ions are ejected from the surface of the liquid. These ions are then extracted into the analyzer of a mass spectrometer for measurement of a mass spectrum. As mixture components emerge from the LC column, their mass spectra are obtained. 

Assay of Enzymes In body fluids, enzyme levels aie measured to help in diagnosis and for monitoiing treatment of disease. Some enzymes or isoenzymes are predominant only in a particular tissue. When such tissues are damaged because of a disease, these enzymes or isoenzymes are Hberated and there is an increase in the level of the enzyme in the semm. Enzyme levels are deterrnined by the kinetic methods described, ie, the assays are set up so that the enzyme concentration is rate-limiting. The continuous flow analyzers, introduced in the early 1960s, solved the problem of the high workload of clinical laboratories. In this method, reaction velocity is measured rapidly the change in absorbance may be very small, but within the capabiUty of advanced kinetic analyzers. 

Various experimental methods to evaluate the kinetics of flow processes existed even in the last centuty. They developed gradually with the expansion of the petrochemical industry. In the 1940s, conversion versus residence time measurement in tubular reactors was the basic tool for rate evaluations. In the 1950s, differential reactor experiments became popular. Only in the 1960s did the use of Continuous-flow Stirred Tank Reactors (CSTRs) start to spread for kinetic studies. A large variety of CSTRs was used to study heterogeneous (contact) catalytic reactions. These included spinning basket CSTRs as well as many kinds of fixed bed reactors with external or internal recycle pumps (Jankowski 1978, Berty 1984.)... 

Both kinetic and equilibrium experimental methods are used to characterize and compare adsorption of aqueous pollutants in active carbons. In the simplest kinetic method, the uptake of a pollutant from a static, isothermal solution is measured as a function of time. This approach may also yield equilibrium adsorption data, i.e., amounts adsorbed for different solution concentrations in the limit t —> qo. A more practical kinetic method is a continuous flow reactor, as illustrated in Fig. 5. 

Continuous flow devices have undergone careful development, and mixing chambers are very efficient. Mixing is essentially complete in about 1 ms, and half-lives as short as 1 ms may be measured. An interesting advantage of the continuous flow method, less important now than earlier, is that the analytical method need not have a fast response, since the concentrations are at steady state. Of course, the slower the detection method, the greater the volumes of reactant solutions that will be consumed. In 1923 several liters of solution were required, but now reactions can be studied with 10-100 mL. 

The dead time is typically 3-5 ms. so stopped flow is not quite as fast as continuous flow, but it requires less than a milliliter of each solution per run. Methods have been described for measuring the dead time " " these are based upon standard reactions whose kinetic behavior is well known. The error introduced by collecting data before mixing is complete can be corrected." ... 

Fig. 9.6 Method of preventing corrosion by premature condensation of acidic vapours. pH measured continuously at point X automatically controls flow of sodium hydroxide...

The Pt film, with a surface area corresponding to NG=4.2-10 9 mol Pt, measured via surface titration of oxygen with C2H4,1,4 is exposed to po2 — 4.6 kPa, PC2H4 = 0.36 kPa at 370°C in a continuous flow gradientless (CSTR) reactor of volume 30 cm3. The rate of C02 formation is monitored via an infrared analyzer.1,4... 

Two types of continuous flow solid oxide cell reactors are typically used in electrochemical promotion experiments. The single chamber reactor depicted in Fig. B.l is made of a quartz tube closed at one end. The open end of the tube is mounted on a stainless steel cap, which has provisions for the introduction of reactants and removal of products as well as for the insertion of a thermocouple and connecting wires to the electrodes of the cell. A solid electrolyte disk, with three porous electrodes deposited on it, is appropriately clamped inside the reactor. Au wires are normally used to connect the catalyst-working electrode as well as the two Au auxiliary electrodes with the external circuit. These wires are mechanically pressed onto the corresponding electrodes, using an appropriate ceramic holder. A thermocouple, inserted in a closed-end quartz tube is used to measure the temperature of the solid electrolyte pellet. 

The time that a molecule spends in a reactive system will affect its probability of reacting and the measurement, interpretation, and modeling of residence time distributions are important aspects of chemical reaction engineering. Part of the inspiration for residence time theory came from the black box analysis techniques used by electrical engineers to study circuits. These are stimulus-response or input-output methods where a system is disturbed and its response to the disturbance is measured. The measured response, when properly interpreted, is used to predict the response of the system to other inputs. For residence time measurements, an inert tracer is injected at the inlet to the reactor, and the tracer concentration is measured at the outlet. The injection is carried out in a standardized way to allow easy interpretation of the results, which can then be used to make predictions. Predictions include the dynamic response of the system to arbitrary tracer inputs. More important, however, are the predictions of the steady-state yield of reactions in continuous-flow systems. All this can be done without opening the black box. 

Washout experiments can be used to measure the residence time distribution in continuous-flow systems. A good step change must be made at the reactor inlet. The concentration of tracer molecules leaving the system must be accurately measured at the outlet. If the tracer has a background concentration, it is subtracted from the experimental measurements. The flow properties of the tracer molecules must be similar to those of the reactant molecules. It is usually possible to meet these requirements in practice. The major theoretical requirement is that the inlet and outlet streams have unidirectional flows so that molecules that once enter the system stay in until they exit, never to return. Systems with unidirectional inlet and outlet streams are closed in the sense of the axial dispersion model i.e., Di = D ut = 0- See Sections 9.3.1 and 15.2.2. Most systems of chemical engineering importance are closed to a reasonable approximation. 

CK catalyzes the reversible phosphorylation of creatine in the presence of ATP and magnesium. When creatine phosphate is the substrate, the resulting creatine can be measured as the ninhydrin fluorescent compound, as in the continuous flow Auto Analyzer method. Kinetic methods based on coupled enzymatic reactions are also popular. Tanzer and Gilvarg (40) developed a kinetic method using the two exogenous enzymes pyruvate kinase and lactate dehydrogenase to measure the CK rate by following the oxidation of NADH. In this procedure the main reaction is run in a less favorable direction. 

Microcosms are laboratory systems generally consisting of tanks such as fish aquaria containing natural sediment and water or soil. In those that have been most extensively evaluated for aquatic systems, continuous flow systems are used. In all of them, continuous measurement of evolved... 

On-line GC analysis (Shimadzu GC 14A) was used to measure product selectivity and methane conversion. Details on the analysis procedure used for batch and continuous-flow operation are given elsewhere [12]. The molecular sieve trap was found to trap practically all ethylene, COj and HjO produced a significant, and controllable via the adsorbent mass, percentage of ethane and practically no methane, oxygen or CO, for temperatures 50-70 C. The trap was heated to -300°C in order to release all trapped products into the recirculating gas phase (in the case of batch operation), or in a slow He stream (in the case of continuous flow operation). 

The simple feedback control system below consists of a continuous-flow stirred tank, a temperature measurement device, a controller and a heater. 

The temperature of a continuous flow of material through a steam-heated stirred tank is controlled by regulating the flow of steam. The tank temperature is measured by a thermocouple set inside a thermowell, giving a delayed temperature measurement response. This example is based on that of Robinson (1975). 

Two different approaches to the use of C02 labeling have been applied to measure carbon flow within plant-soil systems—pulse-chase and continuous labeling. 

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