Triphenyl Tin Chloride (as Sn) (5527)
TRIPHENYL TIN CHLORIDE (as Sn) 5527 C18H15ClSnMW: 385.46CAS: 639-58-7RTECS: WH6860000 |
| METHOD: 5527, Issue 1 |
EVALUATION: PARTIAL |
Issue 1: 15 March 2003 |
| OSHA: 0.1 mg / m3 as Sn | PROPERTIES:solid; MP 108 °C; BP 240°°C |
| NIOSH: 0.1 mg / m3 as Sn (skin) | |
| ACGIH: 0.1 mg / m3 as Sn |
|
| SYNONYMS: Chlorotriphenylstannane, Chlorotriphenyltin, Fentin Chloride, Triphenylchlorostannane, Triphenylchlorotin |
| SAMPLING | MEASUREMENT |
| SAMPLER: FLOW RATE: VOL-MIN: -MAX: SHIPMENT: SAMPLE STABILITY: BLANKS: |
FILTER (37-mm, 5-µm polyvinyl chloride) 1 to 4 L / min 100 L 2000 L Routine Stable at ambient temperature for 28 days 2 to 10 field blanks per set |
TECHNIQUE: ANALYTE: FILTER DESORPTION: SEPARATION: ICP: DETECTOR WAVELENGTH: INJECTION VOLUME: CALIBRATION: RANGE: ESTIMATED LOD: PRECISION (Ŝr): |
HIGH PERFORMANCE LIQUID CHROMATOGRAPHY (HPLC) / INDUCTIVELY COUPLED ARGON PLASMA ATOMIC EMISSION SPECTROSCOPY (ICP-AES) Tin 5 mL tropolone/water/methanol (0.02:22:78) HPLC, reverse phase; C18), 250 x 4.60-mm, 5-μm, Kingsorb 5 or equivalent Operating under conditions for organic compound 189.9 nm 50 μL Standard solutions of triphenyl tin chloride in methanol 10 μg to 225 μg per sample [1] 3 μg per sample (instrumental) [1] 0.034 [1] |
| ACCURACY | |||
| RANGE STUDIED: BIAS: OVERALLPRECISION (ŜrT): ACCURACY: |
Not studied Not determined Not determined Not determined | ||
| APPLICABILITY: The working range of this method is 0.01 to 0.2 mg/m3 as tin in a 1000 L air sample. |
| INTEREFERENCES: Other organotin compounds with the same retention time as triphenyl tin chloride would interfere. |
| OTHER METHODS: There are no other NIOSH methods specifically for triphenyl tin chloride. Other organotin compounds have been determined by NIOSH Method 5504 [2] which uses the analytical technique of HPLC-atomic absorption spectroscopy. |
REAGENTS:
EQUIPMENT:
1. Tropolone (2-Hydroxy-2,4,6cycloheptatrienone) min. 99% pure. 2. Glacial Ac etic Acid, T race M etal G rade .* 3. Me than ol, HP LC Grade .* 4. Triphenyl tin chloride*, 95% pure. 5. Deionized, distilled water. 6. Mobile Phase: 0.020%(w/v)tropolone, 22%(v/v) water, 6.0% (v/v) acetic acid, 72% (v/v) m etha nol [3]. 7. De sorbing solution: 0.020% (w/v)tropo lone, 22%(v/v) w ate r, 78% (v/v) m eth anol. 8. Triphenyl tin chloride standard solution, 200 µg/m L (as tin) with m etha nol as solve nt. 9. Ca libration c urve solutions: P ipet approp riate am ounts of triphenyl tin chloride standard solution into 1 0-m L volum etric flas ks to prepare solutions that are 1, 5, 15, 25, 35, and 45 µg/mL (as tin). Add desorbing solution to the m ark . 10. Argon. 11. Ox ygen.
1. Sam pler: po lyvinyl chloride filter with su ppo rt pad s (3-µm , 5-µm obtainable from SKC, Inc ., Eighty Four, PA 15330 , Cat. No. 225-8-01-1) in cassette filter holder. 2. Personal sa m pling pum p, 1 to 4 L/m in, with flexible connecting tubing. 3. High performance liquid chromatograph (HPLC) with reverse phase column (Kingsorb 5 C 18, 250 x 4.60-mm , 5-micron, or equivalent), guard column (Alltima 10 mm X 4.60-m m C 18, 5-m icron) an d 50-µL sam ple loop injector. 4. Ind uctively coupled arg on plasm a-ato m ic emission spectrometer equipped for analysis of organic com pounds (See AP PEN DIX). 5. Regulators for argon and for oxygen. 6. Bea kers : Griffin, 50-m L. ** 7. Volum etric flasks : 10-, 100- a nd 10 00-m L.** 8. Syringe, 100-µL. 9. Ultrasonic bath. 10. Pipets, various sizes for standard preparation. 11. Polystyrene (8-m L) round bottom tubes with caps. 12. Pla stic film . 13. Forceps.
- See SPECIAL PRECAUTIONS
- Clean all glasswa re with conc. nitric acid
and rinse thorough ly with distilled water.
SPECIAL PRECAUTIONS: Triphenyl tin chloride is highly toxic and readily absorbed through skin. Avoid bre ath ing dust a nd wear gloves when workin g with it and its solution s. C oncentrate d acetic acid is corrive, and a skin and eye irritant. Methanol is flamm able and toxic.
SAMPLING: 1. Calibrate each personal sampling pump with a representative sampler in line. 2. Sam ple at a n ac curately kn own flow ra te betwee n 1 and 4 L/m in for a total sam ple size of 10 0 to 1000 L.
SAMPLE PREPARATION: 3. Open the cassette filter holders and, with tweezers, transfer the samples and blanks to clean beakers. 4. Ad d 5 m L of de sorbing solution. C over with plastic film . 5. Agitate be akers in an u ltrasonic ba th for 5 m in. 6. Transfer the solutions to polystyrene tubes. Cap.
CALIBRATION AND QUALITY CONTRO L: 7. Calibrate with six working standards in the range of 5 to 225 µg as tin per sample. a. Pipet kno wn a m oun ts of triphen yl tin chloride stoc k solution into 10-m L volum etric flas ks . Dilute NIOSH Manual of Analytical Methods (NMAM), Fourth Edition TR IPHEN YL TIN CH LOR IDE: ME TH OD 5527, Issue 1, dated 1 5 Ma rch 2003 - Page 3 of 5 with desorbing solution. b. Analyze sam ples and blank s (steps 10 an d 11). c. Prepare a calibration graph (pe ak area vs µg Sn ). 8. One day before analyzing samples, prepare three spiked media blanks. Desorb (steps 3 through 6) and analyze with standards and blanks. 9. Analyze three quality control blind spikes and three analyst spikes to check calibration graph.
MEASUREMENT: 10. Set ICP for analysis of organic compounds according to manufacturer’s specifications. 11. Operate HPLC under the following conditions: a. C 18 column b. Flush column with approximately 30 mL of mobile phase before connecting to ICP c. Mobile phase flow rate: 1 m L/m in d. After ICP is ready for analysis, connec t effluent from HP LC to ICP spra y cham ber. 12. Injec t standard s, sa m ples, and blank s on to HPLC colum n an d rec ord c hrom atog ram s.
CALCULATIONS: 13. Analyze chrom atog ram s us ing a c onvenient HPLC software p rogram . 14. Cons truct a calibration graph (pe ak area versus µg of tin). 15. From calibration graph determine the mass in µg of tin for each sample (W ) and for the average m edia blank (B). Calculate the conc entration, C, of tin in the volume o f air samp led, V (L):
NOT E: µg/L m g/m 3
EVALU ATION OF M ETH OD : This method was developed in response to an increased use of organotin compounds in the workplace and to test the applicability of the hyphenated technique of HPLC-ICP-AES for their analysis. Triphenyl tin chloride, the compound of this method, is a pesticide and an antifouling agent for paints. ICP instrum ents a re typically set up fo r the analysis of in organic m eta l com pounds. W hen one is used as a detector for organo-metal compounds in the effluent of an HPLC instrument, certain modifications of the operating con ditions of the ICP m ust be co nsidered . Its torch and spray chamber m ust be suited to the analysis of organic com pounds and gas flow rates are different for analysis of solution s contain ing org anic compounds. Such information can be obta ined from the m anufacturer of a specific ICP instrument. In addition, oxygen gas is introduced into the plasma to prevent the formation of carbon deposits. This method was evaluated for limit of detection (LOD), linear range, and sample stability [1]. An instrumental LOD of 3 µg as tin per sample was determined. This corresponds to a Lim it of Quantita tion that is approximately 0.1 x the Permissible Exposure Limit (PEL). Calibration standards showed the method to be linear to an upper limit of approximately 240 µg per sample which is equivalent to 2.4 times the PEL. Samples with higher concentrations were not tested. The method was further evaluated by a recovery study using spiked lab sam ples on polyvinyl chloride filters that contained triphenyl tin chloride at four levels in the range of 9.5 to 190 µg as tin per sam ple. This range is from approxim ate ly 0.1 to 2 x the PEL. At each level six filters were analyzed. Recoveries ranged from 97% to 100% with an average RSD of 0.034. Filters were also spiked at 95 µg/sample and stored at room temperature for 7, 14, and 28 days. Recoveries ranged from 96% to103% with an average RSD of 0.032. NIOSH Manual of Analytical Methods (NMAM), Fourth Edition TR IPHEN YL TIN CH LOR IDE: ME TH OD 5527, Issue 1, dated 1 5 Ma rch 2003 - Page 4 of 5
REFERENCES: [1] [2] [3]
Hopkins BM [2002] Backup data report for Triphenyl Tin Chloride, August 15, 2002, (unpublished report). NIOSH/DART. NIO SH [1994]. NIO SH Ma nua l of Analytical Metho ds, 4 th ed., Method 5504, DHHS(NIOSH) Publication 94-113 (August 1994) Dauchy X, Cottier R, Batel A, Jeannot R, Borsier M, Astruc A, Astruc M [1993]. Mobile phase composition based on speciation of butyltin compounds by high-performance liquid chromatography with inductively coupled plasma m ass spectrometry detection. J Chromatogr Sci 31: 416-421.
METHOD WRITTEN BY: Barbara M. Hopkins, Ph.D. NIOSH/DART
APP EN DIX : Ope ration of ICP -HPL C Instrum ent: ICP conditions refer specifically to the Spectroflame EOP. 1. Install torch and s pray cham ber for an alysis of orga nic com pou nds into ICP instrum ent. 2. Co nne ct inlet tub ing for organic ana lysis to sp ray cham ber a nd d irect IC P waste into a suitable was te container. 3. Once argon is flowing through instrument adjust gas pressures so that nebulizer pressure is 2.2 bar and auxiliary gas flow rate is 23 SKT. 4. Set valve for switching between pumping aqueous solutions and organic solvents to position for aqueous. Allow water to pump through system while following typical procedures for lighting the torch. Light torch and allow system to warm up for 30 minutes. 5. Start mobile phase pumping through HPLC instrument at a flow rate of 1 ml/min. Check for correct flow rate. 6. After warm-up period, profile the optics on the ICP using an aqueous solution that is 10 ppm Cd +2, 10 ppm Li +1, and 50 ppm Zn +2. 7. Following successful profiling, open the valve on the oxygen tank and then change certain settings on the ICP under INSTR UMEN T PARAM ETERS (a subset of OPERAT IONS) so that the following are applied: GENERATOR PARAMETERS Plasm a Powe r (W ) Pum p Step Coolant Step Auxiliary Step Nebulizer Step Heating SPECIAL VALVE Flush Step
1500 2 5 1 1 0
2
8. Change the position of the valve for switch ing betwe en pum ping aqueous solutions and organic solvents to the position for organic and connect the tubing from the ICP to the end of the HPLC column. Check the valve on the inside of the ICP side panel for leaks. 9. Allow mobile phase to run through ICP for about 10 min before injecting. 10. Plug in sample loop position controller being sure that it is in Position A. 11. In order to obtain a transient scan, select SCAN MANAGER, SCAN, TRANSIENT SCAN on ICP computer. Type in the name of the sample, the measure time (100), the interval time (600), and the num ber of points (999). Select the Sn line (189.9 nm ). 12. Inject a sample of methanol (about 70 :L) into the 50 :L sample loop. Simultaneously push the button on the sam ple injector and the STA RT button on the com puter. 13. After the sample loop controller has moved from Position B back to Position A, remove the syringe. 14. Upon com pletion of the scan, save the scan on a floppy disc. 15. Inject standards and unknowns in triplicate following procedures 11-14.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition TR IPHEN YL TIN CH LOR IDE: ME TH OD 5527, Issue 1, dated 1 5 Ma rch 2003 - Page 5 of 5 16. 17. 18. 19.
After the last injection, disconnect HPLC column from ICP instrument, and allow water to run through the ICP for 15 min. Flush HPLC column with a mixture of 70% methanol and 30% water and cap. Close oxygen valve and change Flush Step setting on ICP to 1. Turn off ICP following typical shut-down procedures.
NIOSH Manual of Analytical Methods (NMAM), Fourth Edition