Thesis (M.S. in Chemical Engineering)--University of California, Berkeley, June 1962. / "UCRL-9987." Includes bibliographical references (leaves 67-68).

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

Calibration methods for quantitative on-site sampling using solid phase microextraction (SPME) were developed based on diffusion mass transfer theory. This was investigated using adsorptive polydimethylsiloxane/divinylbenzene (PDMS/DVB) and Carboxen/polydimethylsiloxane (CAR/PDMS) SPME fiber coatings with volatile aromatic hydrocarbons (BTEX: benzene, toluene, ethylbenzene, and o-xylene) as test analytes. Parameters that affected the extraction process (sampling time, analyte concentration, water velocity, and temperature) were investigated. Very short sampling times (10-300 s) and sorbents with a strong affinity and large capacity were used to ensure a 'zero sink' effect calibrate process. It was found that mass uptake of analyte changed linearly with concentration. Increase of water velocity increased mass uptake, though the increase is not linear. Temperature did not affect mass uptake significantly under typical field sampling conditions. To further describe rapid SPME analysis of aqueous samples, a new model translated from heat transfer to a circular cylinder in cross flow was used. An empirical correlation to this model was used to predict the mass transfer coefficient. Findings indicated that the predicted mass uptake compared well with experimental mass uptake. The new model also predicted rapid air sampling accurately. To further integrate the sampling and analysis processes, especially for on-site or <i>in-vivo</i> investigations where the composition of the sample matrix is very complicated and/or agitation of the sample matrix is variable or unknown, a new approach for calibration was developed. This involved the loading internal standards onto the extraction fiber prior to the extraction step. During sampling, the standard partially desorbs into the sample matrix and the rate at which this process occurs, was for calibration. The kinetics of the absorption/desorption was investigated, and the isotropy of the two processes was demonstrated, thus validating this approach for calibration. A modified SPME device was used as a passive sampler to determine the time-weighted average (TWA) concentration of volatile organic compounds (VOCs) in air. The sampler collects the VOCs by the mechanism of molecular diffusion and sorption on to a coated fiber as collection medium. This process was shown to be described by Fick's first law of diffusion, whereby the amount of analyte accumulated over time enable measurement of the TWA concentration to which the sampler was exposed. TWA passive sampling with a SPME device was shown to be almost independent of face velocity, and to be more tolerant of high and low analyte concentrations and long and short sampling times, because of the ease with which the diffusional path length could be changed. Environmental conditions (temperature, pressure, relative humidity, and ozone) had little or no effect on sampling rate. When the SPME device was tested in the field and the results compared with those from National Institute of Occupational Health and Safety (NIOSH) method 1501 good agreement was obtained. To facilitate the use of SPME for field sampling, a new field sampler was designed and tested. The sampler was versatile and user-friendly. The SPME fiber can be positioned precisely inside the needle for TWA sampling, or exposed completely outside the needle for rapid sampling. The needle is protected within a shield at all times hereby eliminating the risk of operator injury and fiber damage. A replaceable Teflon cap is used to seal the needle to preserve sample integrity. Factors that affect the preservation of sample integrity (sorbent efficiency, temperature, and sealing materials) were studied. The use of a highly efficient sorbent is recommended as the first choice for the preservation of sample integrity. Teflon was a good material for sealing the fiber needle, had little memory effect, and could be used repeatedly. To address adsorption of high boiling point compounds on fiber needles, several kinds of deactivated needles were evaluated. RSC-2 blue fiber needles were the more effective. A preliminary field sampling investigation demonstrated the validity of the new SPME device for field applications.

Heat actuated adsorption heat pumps offer the opportunity to improve overall energy efficiency in waste heat applications by eliminating shaft work requirements accompanying vapor compression cycles. The coefficient of performance (COP) in adsorption heat pumps is generally low. The objective of this thesis is to model the adsorption system to gain critical insight into how its performance can be improved. Because adsorption heat pumps are intermittent devices, which induce cooling by adsorbing refrigerant in a sorption bed heat/mass exchanger, transient models must be used to predict performance. In this thesis, such models are developed at the adsorbent particle level, heat/mass exchanger component level and system level. Adsorption heat pump modeling is a coupled heat and mass transfer problem. Intra-particle mass transfer resistance and sorption bed heat transfer resistance are shown to be significant, but for very fine particle sizes, inter-particle resistance may also be important. The diameter of the adsorbent particle in a packed bed is optimized to balance inter- and intra-particle resistances and improve sorption rate. In the literature, the linear driving force (LDF) approximation for intra-particle mass transfer is commonly used in place of the Fickian diffusion equation to reduce computation time; however, it is shown that the error in uptake prediction associated with the LDF depends on the working pair, half-cycle time, adsorbent particle radius, and operating temperatures at hand. Different methods for enhancing sorption bed heat/mass transfer have been proposed in the literature including the use of binders, adsorbent compacting, and complex extended surface geometries. To maintain high reliability, the simple, robust annular-finned-tube geometry with packed adsorbent is specified in this work. The effects of tube diameter, fin pitch and fin height on thermal conductance, metal/adsorbent mass ratio and COP are studied. As one might expect, many closely spaced fins, or high fin density, yields high thermal conductance; however, it is found that the increased inert metal mass associated with the high fin density diminishes COP. It is also found that thin adsorbent layers with low effective conduction resistance lead to high thermal conductance. As adsorbent layer thickness decreases, the relative importance of tube-side convective resistance rises, so mini-channel sized tubes are used. After selecting the proper tube geometry, an overall thermal conductance is calculated for use in a lumped-parameter sorption bed simulation. To evaluate the accuracy of the lumped-parameter approach, a distributed parameter sorption bed simulation is developed for comparison. Using the finite difference method, the distributed parameter model is used to track temperature and refrigerant distributions in the finned tube and adsorbent layer. The distributed-parameter tube model is shown to be in agreement with the lumped-parameter model, thus independently verifying the overall UA calculation and the lumped-parameter sorption bed model. After evaluating the accuracy of the lumped-parameter model, it is used to develop a system-level heat pump simulation. This simulation is used to investigate a non-recuperative two-bed heat pump containing activated carbon fiber-ethanol and silica gel-water working pairs. The two-bed configuration is investigated because it yields a desirable compromise between the number of components (heat exchangers, pumps, valves, etc.) and steady cooling rate. For non-recuperative two-bed adsorption heat pumps, the average COP prediction in the literature is 0.39 for experiments and 0.44 for models. It is important to improve the COP in mobile waste heat applications because without high COP, the available waste heat during startup or idle may be insufficient to deliver the desired cooling duty. In this thesis, a COP of 0.53 is predicted for the non-recuperative, silica gel-water chiller. If thermal energy recovery is incorporated into the cycle, a COP as high as 0.64 is predicted for a 90, 35 and 7.0°C source, ambient and average evaporator temperature, respectively. The improvement in COP over heat pumps appearing in the literature is attributed to the adsorbent particle size optimization and careful selection of sorption bed heat exchanger geometry.