Contact time measurements

Clearly, in order to correctly apply CP pulse sequences for quantitative analysis (or even qualitative analysis), many relaxation processes (Tic, T pH, Till. TCp) must be considered and spectral acquisition parameters appropriately set. While a CP spectrum may be obtained when Tic > 7) 11 3TlpH Tqp, a quantitative CP spectrum requires that the recycle delay is sufficient (on the order of Tm) for the protons to be uniformly relaxed at the beginning of the contact time,25 all proton magnetization spin locked in the rotating frame decays at the same rate (T ph), and the contact time is sufficient to allow complete cross polarization (at least 5 times the longest TCp)26 Except when relative peak intensities are constant and appear to be correct, single contact time measurements should be avoided. Instead, 13C spectra and relaxation times should be measured and complete magnetization curves analyzed. 

Regenerate the resin at a flow rate that allows at least forty-five minutes of contact time. Measure the ion concentration of the spent regenerate to determine the... 

For experiments in which the temperature was varied, the temperature was increased stepwise with constant feed composition and total flow. For determining the effect of contact time, measurements were made at a series of total flows between 50 - 300 cm min" with either 100 or 250 mg of catalyst. The flow was varied in a random way rather than sequentially, to avoid any bias in the data. Similarly, for determining the effect of reactant concentration, the concentration of one reactant was varied in a non-sequential manner, while the concentration of the other reactants was kept constant. The catalyst was treated with 20% 02/He for 15 min at 480°C between experiments using different hydrocarbons to remove any hydrocarbon residues from the catalyst. 

Some have argued that the clarifier itself acts as a reactor with a contact time measured in hours. This is a fallacy when applied to the clarified brine portion. Most of the separation between sludge and supernatant brine takes place quickly. The solids population in the clear brine is very low, and there is little opportunity for particle growth. Any further reaction in the clarified brine therefore tends to give particles that are too small to settle. 

The time average bubble contact time measured by F-OPT (s) Local metric tensor Curvature tensor (m )... 

Catalyst Activity. Of utmost importance in the design of most catalysts is activity, which is a measure of the ability of a catalyst to effect conversion of the reactant(s) to the desired product(s) under specified conditions. In industrial applications, catalyst activity is usually discussed in terms of the percent conversion of a reactant under given conditions of temperature, pressure, and contact time. 

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.)... 

Several manual and continuous analytical techniques are used to measure SO2 in the atmosphere. The manual techniques involve two-stage sample collection and measurement. Samples are collected by bubbling a known volume of gas through a liquid collection medium. Collection efficiency is dependent on the gas-liquid contact time, bubble size, SO2 concentration, and SO2 solubility in the collection medium. The liquid medium contains chemicals which stabilize SO2 in solution by either complexation or oxidation to a more stable form. Field samples must be handled carefully to prevent losses from exposure to high temperatures. Samples are analyzed at a central laboratory by an appropriate method. 

Mangipudi et al. [63,88] reported some initial measurements of adhesion strength between semicrystalline PE surfaces. These measurements were done using the SFA as a function of contact time. Interestingly, these data (see Fig. 22) show that the normalized pull-off energy, a measure of intrinsic adhesion strength is increased with time of contact. They suggested the amorphous domains in PE could interdiffuse across the interface and thereby increase the adhesion of the interface. Falsafi et al. [37] also used the JKR technique to study the effect of composition on the adhesion of elastomeric acrylic pressure-sensitive adhesives. The model PSA they used was a crosslinked network of random copolymers of acrylates and acrylic acid, with an acrylic acid content between 2 and 10%. 

Fig. 22. Nomialized pull-off energy measured for polyethylene-polyethylene contact measured using the SFA. (a) P versus rate of crack propagation for PE-PE contact. Change in the rate of separation does not seem to affect the measured pull-off force, (b) Normalized pull-off energy, Pn as a function of contact time for PE-PE contact. At shorter contact times, P does not significantly depend on contact time. However, as the surfaces remain in contact for long times, the pull-off energy increases with time. In seinicrystalline PE, the crystalline domains act as physical crosslinks for the relatively mobile amorphous domains. These amorphous domains can interdiffuse across the interface and thereby increase the adhesion of the interface. This time dependence of the adhesion strength is different from viscoelastic behavior in the sense that it is independent of rate of crack propagation.

Step 2. After a contact time t, the material is fractured or fatigued and the mechanical properties determined. The measured properties will be a function of the test configuration, rate of testing, temperature, etc., and include the critical strain energy release rate Gic, the critical stress intensity factor K[c, the critical... 

Measurements of the true reaction times are sometimes difficult to determine due to the two-phase nature of the fluid reactants in contact with the solid phase. Adsorption of reactants on the catalyst surface can result in catalyst-reactant contact times that are different from the fluid dynamic residence times. Additionally, different velocities between the vapor, liquid, and solid phases must be considered when measuring reaction times. Various laboratory reactors and their limitations for industrial use are reviewed below. 

Induction period measurements can also be used to determine interfacial tensions. To validate the values inferred, however, it is necessary to compare the results with an independent source. Hurley etal. (1995) achieved this for Cyanazine using a dynamic contact angle analyser (Calm DCA312). Solid-liquid interfacial tensions estimated from contact angle measurements were in the range 5-12 mJ/m which showed closest agreement with values (4—20mJ/m ) obtained from the log-log plots of induction time versus supersaturation based on the assumption of — tg. 

Foust et al. (F4) measured gas holdup in mechanically stirred gas-liquid contactors of various diameters (from 1 to 8 ft) and various liquid contents (from 5 to 2250 gal). The nominal gas velocity varied from 1 to 5 ft/min and the power input from 0.01 to 6.5 hp. The contact time (sec/ft) could be correlated by the following expression ... 

Anderson (A2) has derived a formula relating the bubble-radius probability density function (B3) to the contact-time density function on the assumption that the bubble-rise velocity is independent of position. Bankoff (B3) has developed bubble-radius distribution functions that relate the contacttime density function to the radial and axial positions of bubbles as obtained from resistivity-probe measurements. Soo (S10) has recently considered a particle-size distribution function for solid particles in a free stream ... 

According to their measurements, the gas holdup increases with the gas velocity but the average contact time drops. This is not surprising, as will be shown. The volumetric gas flow rate is... 

As mentioned in Section 11.3, fluidized-bed reactors are difficult to scale. One approach is to build a cold-flow model of the process. This is a unit in which the solids are fluidized to simulate the proposed plant, but at ambient temperature and with plain air as the fluidizing gas. The objective is to determine the gas and solid flow patterns. Experiments using both adsorbed and nonadsorbed tracers can be used in this determination. The nonadsorbed tracer determines the gas-phase residence time using the methods of Chapter 15. The adsorbed tracer also measures time spent on the solid surface, from which the contact time distribution can be estimated. See Section 15.4.2. 

Literature references and the measurement of the contact time distribution in a large, cold-flow model of a gas-fluidized bed are reported in... 

The yield of a gas-solid heterogeneous reaction depends not on the total time that molecules spend in the reactor but on the time that they spend on the catalyst surface. The contact time distribution provides a standardized measure of times spent in the absorbed state. A functional definition is provided by the following equation applicable to a first-order, heterogeneous reaction in an isothermal reactor ... 

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