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MEASUREMENT of STIBINE and ARSINE GENERATION from the EXIDE 3100-Ah LEAD-ACID MODULE

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MEASUREMENT of STIBINE and ARSINE GENERATION from the EXIDE 3100-Ah LEAD-ACID MODULE Chemical Technology ANL-87-1 Division Chemical Technology Division Chemical Technology L/.r. ,ion Chemical Technology Di'; ..on Chemical Technology Measurement of Stibine and Division Chemical Technology Arsine Generation from the Division Exide 3100-Ah Lead-Acid Module Chemical Technology Division Chemical Technology D . ion by J. J. Marr and J. A. Smaga Chemical Technology Division Chemical Technology Division Chemical Technology Division Chemical Technology Division Chemical Technology Division Chemtcai Technology Division Chemical Technology Division Chemical Technology Division Chemical Technology Division Argonne National Laboratory, Argonne, Illinois 60439 operated by The University of Chicago for the United States Department of Energy under Contract W-31-109-Eng-38 Chemical Technology Division Chemical Technology Division Chemical Technology Division Chemical Technology Division charged at a constant current of 512 A. After approximately four hours, the module reached a prescribed voltage (adjusted for the temperature of the module) and was held at this voltage until the current decayed to about 155 A. The current was maintained at this level until the total charge passed was equivalent to 110% of the ampere-hours discharged during the previous cycle- Every thirteenth cycle, the module typically received an equalization charge, which extended the finishing charge an additional 10%. The cycles selected for sample collection occurred at least five cycles after an equalization charge to ensure that the measured hydride levels were not influenced by any residual effects of equalization. Each cell was sampled ten times during the charge cycle, with an addi­ tional sample taken during the initial portion of the next discharge cycle. The first sample interval began at a cell voltage of 2.35 V. The sampling interval was progressively shortened as the voltage approached 2.5 V, and then lengthened once this value was exceeded. The gas samples were collected con­ tinuously by switching between the two gas trains. Each time, before trans­ ferring the samples to labeled storage bottles, the gas line and the space above the absorbing solution in the bubblers were purged with helium for two to three minutes to remove any traces of residual toxic gases. Samples from both bubblers were then analyzed for stibine and arsine. 2.3 Chemical Analyses Antimony was determined by decoloring an aliquot of absorbing solution with hypophosphite and measuring the Sbl^' concentration by spectrophotometric analysis. The concentration of antimony in the aliquot was determined by comparing the aliquot absorbance to the absorbance of solution standards con­ taining known quantities of antimony. The arsenic concentration was measured with an atomic absorption spectrophotometer that was equipped with a hydride generation system for the reconversion of the arsenic to arsine. The arsine was swept into the flame, and the peak height of the absorbance was measured. The amount of arsenic in the sample was determined from a working curve that related the peak height to calibration standards. The sensitivity of these methods was 10 yg SbHj and 1 pg of AsHj for each 100 mL of absorbing solution. 3.0 RESULTS AND DISCUSSION 3.1 Hydride Generation Curves The rates of stibine and arsine generation in units of gg/min are plotted as a function of charging time in Figs. 2 through 4. Variations in both the cell voltage and the charge current are also shown in these figures. The rates of hydride generation rapidly increase after the threshold voltage of 2.4 V, reach a maximum value shortly after exceeding this voltage, and decline to lower levels during the balance of the charge cycle. For all three cells, the maxima in the arsine generation rates precede the maxima in the stibine generation rates. The former occurred within a voltage range of 2.51 to 2.52 V, while the latter occurred within a voltage range of 2.53 to 2.54 V. The maxima and subsequent decays to lower generation rates are thought to reflect (1) depletion of antimony and arsenic concentrations built up at the negative plates prior to reaching the threshold voltage for hydride evolution and (2) inadequate replenishment of these species during the balance of the charging period. t«0 1 1 500 VOLTAOI 400 t.sol— < 900 H X — III 200 1 CUKRCMT 100 Pig. 2. 0 __ Stibine and Arsine Generation Rates, Current, and Voltage vs Charging Time for Cell 1. 200 900 400 500 CHARGING TIME, mte 2 60 500 400 H 900 H 200 I CURRENT — too Fig. 3 — 0 2 90 Stibine and Arsine Generation Rates, Current, and Voltage vs. Charging 20K 200 TiM for Cell 3. SbH, I "^ ISO I 7 12I— — 100 A«H «A — 50 0 200 300 400 500 CHARGING TIME, mm 500 —I 400 300 o: 200 c o 100 0 Fig. 4. Stibine and Arsine Generation — 200 Rates, Current, and Voltage vs Charging Time for Cell 5. SbH — 150 00 AsH — 50 200 300 400 500 CHARGING TIME, mm Figures 5 and 6 are the rate profiles for stibine and arsine, respec­ tively. For stibine, the maxima in the profiles are closely grouped and average 215 ±7 yg/min. As charging progresses, the rates decline from these maxima and reach values at the end of charge that are 10 to 25% lower than the peak rates. The maxima in the rate profiles for arsine average 19.7 +1.5 Mg/min. These profiles show sharper declines from the maxima, and they approach or achieve constant values by the end of charging that are 50 to 70% lower than their peak rates. Qualitative agreement exists among the profiles shown here and the rate curves reported for stibine^'^ and arsine^ evolution from different cells. 3.2 Characterization of Hydride Generation The cumulative amounts of stibine and arsine collected from each cell are presented in Table 1. Included in these amounts are the low concentrations of hydrides that were present in the final samples; these samples were collected during the one-hour open-circuit interval that followed charging. Typically, the quantities of both arsine and stibine in the final samples were -2% of the total amounts. These low concentrations undoubtedly reflect the delays in clearing the air space within the cells of remaining hydrides and in trans­ porting these gases through the collection system. On average, 19 mg of stibine and 1.4 mg of arsine were generated during each charge cycle. 230 200 — 150 — g '00 K 500 CHARGING TIME, min Fig. 5. Rate Profiles for Stibine Generation Table 1 also lists three additional parameters, including previously dis­ cussed peak rates, that characterize the degree of hydride generation. To derive average generation rates, the total quantities of stibine and arsine vere divided by the duration of the constant-current finishing charge. This duration was variable and ranged from 101 to 119 minutes for the three cycles of interest. The average value for the three stibine rates was 175 ±4 ug/min. Sinilarly, the average of the arsine rates was 12.6 ±1.0 yg/min. The third parameter, terned the "overcharge rate** in this report, was determined by dividing the total hydride weight by the ampere-hours of overcharge ('-250 Ah). The averages for the overcharge rates are 75.8 ± 9.5 and 5.46 ± 0.81 yg/Ah for stibine and arsine, respectively. 22 20 18 16 14 12 I 10 (A < 200 300 400 500 CHARGING TIME, min Fig. 6. Rate Profiles of Arsine Generation The overcharge rates were calculated in order to compare results with an earlier study discussed in Section 4.16 of the Exide report.^ In that study, test cells with a rated capacity of 400 Ah were subjected to a continuous overcharge at 30 A as an accelerated method of determining grid corrosion and hydride evolution rates. One cell in the test group contained positive plates with the same composition as the six-cell module and positive grids (4% Sb-0.05% As-bal. Pb) similar in composition to the proprietary alloy used in the module. After 40 kAh of overcharge at 50 to 55**C, the average over­ charge rates for the accelerated tests were 52 and 2.6 yg/Ah for stibine and arsine, respectively. These values are 31% lower for stibine and 52% lower for arsine than the comparable average rates for the module cells. Table 1. Stibine and Arsine Generation for Each Cell Cell Total Velght, Peak Rate, Average Rate, Overcharge Rate, No. mg Mg/"in pg/min Ug/Ah Stibine 1 21.34 218 179 85.3 3 18.17 208 173 72.9 5 17.40 220 172 69.1 Arsine 1 1.50 18.3 12.6 5.98 3 1.43 21.2 13.6 5.74 5 1.17 19.7 11.6 4.65 A nuaber of experimental differences vere considered in attempting to explain the disparity between the accelerated overcharge rates and the cycled overcharge rates. Two factors, cell temperature and finishing current, can be discounted for the following reasons. During the cycles that measurements vere made on the module, the cell temperatures ranged from 42.5 to 47.2^C, or roughly 7 to 8^C lover than the average temperature for the accelerated tests; the complete Exide study^ and other studies^'^^ indicate that lover test tem­ peratures reduce arsine and stibine evolution. Additionally, vhen the fin­ ishing currents are normalized for the differences in rated capacity, the charging regime used for the accelerated tests vas more severe than the module charge, 0.075 A per Ah versus 0.050 A per Ah. The indications from other vork^'^ are that lover finishing currents, vhich also mean lover voltages, also reduce hydride evolution. Other factors, one of vhich is specifically related to arsine evolution, may account for the variation betveen module and accelerated overcharge rates.
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