| Brecon HP 5972A Mass Selective Detector HP 5972A MSD Update Documentation For Internal Use OnlyNotice The information in this document is subject to change without notice. ‘Hewlett-Packard makes no warranty of any kind, expressed or implied, including, but not limited to, the implied warranties of merchantability and fitness for a particular purpose. Hewlett-Packard shall not be liable for errors contained herein or for incidental or consequential damages (including lost profits) in ‘connection with the furnishing, performance, or use of this material whether based on warranty, contract or other legal theory. Hewlett-Packard assumes no responsibility forthe use or reliability of its software on equipment that is not famished by Hewlett-Packard. ‘This document contains proprietary information which is protected by copyright. All rights reserved. No part of this document may be photocopied, reproduced without the prior writen consent of Hewlett-Packard Company. Copyright 1993 by Hewlett-Packard Company Hewlett-Packard Company Scientific Instruments Division ‘MS Product Support 1601 California Ave. Palo Alto, CA 94304Table of Contents 1 Introduction ....... ee TM —_-HP5972A Hardware Features . Interface Capillary Direct .. Jet Separators ........+ Effluent Splitter .. S9T2AMRD Interface . Source .. Filaments ... Repeller Source Cable Assembly Mass Filter ....... Detector ‘Vacuum System ‘Vacuum Manifold Manifold O-ring .. Top Plate .. Ton Gauge Port Calibration Valve Assembly . Diffusion Pump . Rough Pump Flow Rates ‘Vacuum Pressures Electronics . SmanCard I Main Board . Top Board ...... Power Supply Board ......... Power/Vac Board Status Display Board ...mm <2 vi vit vill Cabinet/Covers .. 15 HP 5972A Tuning .... seveeeeee . 16 Maximum Sensitivity Autotune . 16 ‘Standard Spectra Autotune ... 18 Quick Tune 18 Typical Autotune Lens Ramps Example Air and Water Checks .. Example Autotune Reports ...... ‘Tune Comparison Charts .. HP 5972A Checkout Procedure . Customer Familiarization Installation and Familiarization Time ....... Software Requirements .. HP 5972A Parts .... Addenda: HP 5972A vs, HP 5971A Charts ‘Mustang 3.5 Features HP 5972A Application Notes HP 5972A Sales Training Manual HP 5972A Installation ManualI Introduction ‘The HP 5972A Mass Selective Detector (MSD), introduced in November 1992, is the latest version of HP's benchtop mass spectrometer. The HP 5972A is a standalone capillary GC detector designed for ‘use with the HIP 5890 Series I Gas Chromatograph. It includes a high efficiency electron impact ion source, monolithic hyperbolic quartz. quadrupole mass filter, quick-change electron multiplier, new drive electronics with the second generation MS control card (SmartCard I1), and a high-reliability vacuum system, ‘The HP 59724 is similar in design to the HP 5971A, yet it incorporates several new features and improvements, This update documentation describes those new features and the differences between the HP 5972A and the HP 5971A. Each functional area of the HP 597A will be presented, and where there haven't been any changes from the HP 5971A it will be indicated. ‘This update documentation also includes information on the different tuning available for an HP '5972A, installation and familiarization time for an HP 5972A, the software required for operating an HP 5972A, and a parts list for the HP 5972A. Addenda with this update documentation include Mustang 3.5 features, HP 5972A application notes, the HP 5972A Sales Training Manual, and the HP 5972A Installation Manual. For additional information on the HP 5972A, order the HP 5972A Hardware Manual, HP part number 05972-90001, available from HP Analytical Direct. ‘This update documentation is for customer engineers who already have been trained on the operation, ‘maintenance and troubleshooting of the HP 59714.Il HP 5972A Hardware Features Interface Capillary Direct ‘The HP 5972A uses the same capillary direct interface with the same parts as the HP S971A. A recent change in the heater sensor assembly to lengthen the sensor cartridge to prevent interface temperature oscillations affects the capillary direct interfaces for both the HP 5972A and the HP 5971A (refer to Service Notes 5972-01 and 5971-24 in the April 1993 issue of the Source). ‘Note; when you replace an old heater sensor assembly with a new one with the longer sensor, you will also need to get a new heater clamp that has a deeper hole for the sensor! ‘Jet Separators ‘The HP 5972A can be configured with either a glass or metal jet separator, HP products 59913A and 59913B, respectively. Effluent Splitter ‘The HP 5972A ships with an effluent splitter in the shipping kit. The effluent splitter is designed for use with 0.32 or 0.53 mm ID columns and can be used as an alternative to the jet separator. The effluent splitter, however, gives a straight split and doesn't have the sample concentrating effect of the jet separator. S9T2A/IRD Interface A longer interface is available for the HP 5972A when it is configured with an IRD. The 5972A/IRD interface ships with the HP $972A when option #060 is ordered.Source ‘The HP 5972A El source incorporates redesigned filaments. The other parts of the source are the same asin the HP 5971A EI source. Filaments ‘The HP 5972A filaments were redesigned to increase the ionization current in the source. The filament is now coiled in the middle to increase its effective length near the hole in the ion source body. ‘This allows for more electrons to be emitted toward the hole and into the ionization chamber. The coils also reduce the tension that the filament is under and will accommodate flexing of the filament, thus prolonging filament life. ‘The HP 5972A filament design includes a reflector which is held at filament potential (-70V dc). ‘The reflector focuses the electrons that are emitted from the filament toward the ionization chamber, resulting in higher ionization currents, In addition to the new filament design, the filament emission current is now variable in the HP 5972. ‘You can change the emission current setting in Manual Tune and save the parameters to a tune file. However, the optimum emission current for the HP 5972A is 50 uA. At higher emission currents, so many electrons may be directed into the ionization chamber that the potential gradient across the ionization chamber created by the repeller voltage will be perturbed and fewer ions will be directed toward the mass filter; at lower emission currents, there will be fewer electrons in the ionization chamber and therefore fewer ions will be generated in the source.‘The optimum filament emission current of SOuA for the HP 5972 compares to a set filament emission current of 200 wA in the HP 5971A. ‘The lower emission current for the 5972A filament results in longer filament life. ‘The HP 5972A filament is made of rhenium wire across stainless steel posts with a ceramic insulator body. HP 5972A filaments will not work in an HP 5971 source; likewise, HP 5971A filaments will not work in an HP 5972A source. Repeller ‘The repeller in the HP 5972A EI source is the same part as in the HP 5971A source, but the potential that can be applied to it has been extended. ‘The new voltage range on the HP 5972A repeller is 0 to +42.9 V, compared to a voltage range of 0 to + 20 V on the HP 5971A repeller. The higher voltage allows for more ions to be directed into the mass filter and therefore more signal. Although the ‘Standard Spectra Autotune will hold the repeller at a fixed voltage (+20 V), the new Maximum, ‘Sensitivity Autotune will ramp the repeller and try to maximize the signal across the mass range. In the HP 5971A EI source, a high ion-current through the repeller was used to detect an "excessive source pressure condition. Since the HP 5972A has higher ionization current and consequently a higher ion current through the repeller, the repeller could no longer be used to sense “excessive source Pressure”, so that fault circuit was eliminated (see the Electronics section, Main Board). Source Cable Assembly Because of the new filament design, there is a new source cable assembly (HP part number 05972-60015) for the HP 5972A.Mass Filter ee — ‘The HP 5972A quadrupole, quadrupole contacts, ceramic end supports and radiator are the same parts as are used in the HP 5971A. The HP 5972A is tested to and can scan to 700 amu, as compared to a scan limit of 650 amu for the HP 5971A. Detector ‘The HP 5972A uses the K&M electron multiplier. The K&M electron multiplier has a dynode which can be snapped out of its bracket for quick replacement. The K&M electron multiplier is the same ‘multiplier that has been shipped standard in the HP 597A since August 1992 (refer to Service Note 5971-23 in the September 1992 issue of the Source)Vacuum System ‘The HP 5972A has a new machined aluminum manifold, a new o-ring seal for the manifold, a different jon gauge tube location, and a different calibration valve configuration. The HP $972A uses the same Edwards E050/60 diffusion pump and Edwards E2M2 rough pump as is used in the HP 59714. ‘Vacuum Manifold ‘The vacuum manifold in the HP 5972A is machined out of a single block of aluminum. This gives a smoother surface to the manifold as compared to a cast manifold and results in reduced background and a shorter time to pump out any moisture that has condensed on the manifold surface. ‘There is an additional opening on the diffusion pump end of the HP 5972A manifold to allow for ‘machining of the baffle region. This opening is sealed by an o-ring and a cap. The cap also has a baffle and "fingers" that extend down into the manifold. The cap was designed to reduce chemical background from the diffusion pump into the analyzer and to facilitate the drainage back into the Eten o leona os oO ee ve os Processor Processor Reno 68 recesses] | Controle As ‘SmartCard II has the following features: 1. Six processors a. main (communications) processor | Motorola 68302 receives data from data processor stores data until itis requested by data system ™ controls real-time events such as opening valves and changing scan or SIM parameters during data acquisition. b. instrument controller ™ integer digital signal processor, mode] ADSP-2101, for instrument control and data sampling "controls scanning of mass filter ™ collects signal data from analog to digital converter and passes that data to the data Processor via a serial bus ™ can dynamically ramp the lens voltages c. data processor ™ digital signal processor, model DSP32C = floating point = digital filtering mass peak detection = unlogging = data packing Bdata sent to main processor through high-speed serial data link 4. serial communication processor = controls communications between main processor and data processor and instrument controller "communicates with main processor through serial bus ™ communicates with data processor and instrument controller through parallel bus = _ responsible for control of instrument controller and data processor e. HP-IB controller ™ manages communication between main processor and data system data sent at a rate of 200 kbytev/sec APG processor = synchronizes run-start signals with GCs, ALSs, and purge and traps 2. WO connectors a. MS backplane b. HP-IB bus ©. APG bus 4. three serial instrument command bus (SICB) connectors ™ one SICB interfaces to status display board e. serial data bus 3. RAM a. data buffer, 2 or 8 Mbyte (2 Mbyte standard) "0.5 Mbyte for SmartCard code, the rest for data buffering . digital signal processor (DSP) RAM, 4 or 16 Mbyte (4 Mbyte standard) Main Board ‘The HP 5972A has a redesigned main board, referred to as the A20 main board. The primary changes with the A20 main board, compared to the A18 main board which is used in the HP 5971A, are the variable filament emission current capability, the elimination of the "excessive source pressure” and “excessive signal level” fault circuits, and the extended voltage range for the repeller DAC. The dynamic range of the log amp on the A20 main board is the same as on the A18 main board: 0 to -20 UA input current produces 0 to +10V output voltage. ‘The A20 main board has an ID bit that allows the data system to recognize the instrument as a 5972A. ‘The A20 main board is not supported in the HP S971A. Top Board ‘The HP 5972A uses the same top board that is used in the HP 5971A. 14Power Supply Board ‘The HP 5972A uses the same power supply board that is used in the HP S971A. Power/Vac Board ‘The HP 5972A uses the same power/vac board that is used in the HP 5971A. Status Display Board Power Analyzer Calvalve ao a a ~ a KI ‘The status display board is new for the HP 972A. ‘The status display board receives signals from the ‘SmartCard II through a serial interface and lights a series of LEDs on the front cover of the instrument indicating the Power, Analyzer and Cal Valve status. The Power LED lights when power is switched ‘on; the Analyzer LED lights when the MSD receives an MSON signal from the data system; the Cal Valve LED lights when the data system instructs the calibration valve to open. Cabinet/Covers ‘The HP 5972A has a new cabinet to accommodate the machined vacuum manifold, It also has new covers: a main cover with status indicator LEDs on the front (see the description of the status display board above) and a separate top cover that snaps off for easier access to the analyzer. The main cover and the electronic boards are secured to the cabinet with torx head screws. ‘The HP 5972A has the following dimensions: 36 H x 17 W x 65 D (cm), (14 x 7 x 26 inches). The HP 5972A is 2 cm taller than the HP 5971A; the width and depth of the HP 5972A and 5971A are the same. 15Til HP 5972A Tuning The 5972 does have some distinct hardware differences from the 5971. However, some of the most dramatic differences are not hardware, but in the tuning macros. Mustang III rev. C.01.05, the only ‘Mustang version compatible with the 5972, has 4 tuning macros available. 5972 Top Parte (Pee ze {) Stendard Spectra Autotune QuickTune Manual Tune. Texget Tun Diagnastiesvacuum Contra figure 1 ‘Shown in the pull down menu figure 1 they are: Max Sensitivity Autotune, Standard Spectra Autotune, Quick Tune and Target Tune. Maximum Sensitivity Autotune Maximum Sensitivity Autotune was developed to give exactly what its name implies: maximum sensitivity! Instead of adjusting parameters to achieve a classic PFTBA spectra (100% 69, 50% 219 and greater than 5% 502), Max Sensitivity autotune maximizes all the masses across the amu range. In the past we have chosen to achieve a greater relative abundance of 502 at the expense of low mass sensitivity. The relative percent of 502 can be less than 1% with the Maximum Sensitivity ‘autotune and not indicate a dirty source or some other analyzer problem. Some customers may have to be re-educated to accept this criteria. Mass 69 is still the base peak and the abundance is typically around 1,000,000 counts, The relative abundance of 219 is hard to specify with this autotune, however the absolute abundance of 219 is typically around 200,000. The important thing to keep in ‘mind when evaluating the results of this autotune is that relative abundance is no longer a meaningful criteria, 16‘The ion focus maximum that comes standard with the instrument is 90. This may be raised by going into the menu shown below in figure 2 and raising the ion focus to a maximum of 100. tions Eile Oj Window Help ERY Za erect ee tee oe Execute Calibrate RampParam AdjParam Max Sensitivity Autotune Standard Spectra Autotune QuickTune Set Nominal 96502. Set Fixed Repeller.. Sct Maximum Repeller... Set Maximum lon Focus. Set Peak Width Target. figure 2 ‘When measuring the ion focus on the HP 5971 with the A-18 main board, the measured voltage is not what appears on the display. The display value has to be multiplied by 2 in order to get the value you would read off the test point (see Service Note 5971-18 in the July 1991 issue of the Source). This is no longer the case on the 5972 with the A-20 main board; now what you see is what you get. The voltage you set in the software will be what you read at the test point. In most cases the ion focus will be set to 90 by Max Sensitivity autotune. ‘The repeller in Max Sensitivity autonune is typically set to 30, the maximum is 42.8. The typical repeller setting on a 5971 with Mustang II was 15. ‘This enormous increase is partly responsible for the superior sensitivity of the 5972. However, in mass spectroscopy a gain in sensitivity usually means a tradeoff being made with respect to resolution. ‘The factory specification for the isotope valley between 502 and 503 on the 5971 was 50%. Because of the increased repeller voltage this specification was changed to 40% for the 5972. Another gain in sensitivity was made by increasing the peak widths from 0.50 to 0.55 in Mustang II. This will also give you poorer resolution. As you can see in figure 2 the peak width targets can be changed as well as the repeller to give better resolution. Max Sensitivity autotune should be used when analyzing clean samples and looking for relatively low levels. With the absolute abundance of 69 at 1,000,000 counts, i's obvious that linear dynamic range would be very narrow. Maximum Sensitivity autotune is required before you run the signal-to-noise check for hexachlorobenzene on the 5972. 7Standard Spectra Autotune ‘Standard Spectra Autotune with Mustang IIT is a very different autotune from Standard Spectra with ‘Mustang II. Standard Spectra with Mustang II is still set up to achieve a “classical” spectrum PFTBA. However, if we returned to the practice of de-tuning the low mass in order to bring up the high mass we would almost totally nullify the sensitivity gains we've made with the 5972. ‘The nominal relative percent 502 in Standard Spectra autotune is set to be 3%. Most instruments will give around 2%, NO 5972 will give more than 5%, even if the source is cold! Drug lab customers who are analyzing for THC or other high mass compounds may need more relative % 502. If you refer to figure 2 you can see that the nominal % 502 can be changed; the maximum value is 8. The repeller maximum in Standard Spectra is 25, and it's typically set to 20 by the tune macro. If a tune that resembles the 5971 with Mustang Il is required, set nominal 502 to 8 %, set the peak widths to 0.50, and do a repeller ramp to determine the optimum value. These changes will, however, decrease the sensitivity of the instrument, The hexachlorobenzene specification of 10 pg witha signal-to noise of 10:1 RMS cannot be achieved with these settings. ‘The ion focus will be set to between 80 to 90 and as stated earlier the repeller will be set between 20-25. Peak splitting is a problem that has been seen in final test with the repeller at 25. The final test specification for the maximum repeller voltage with Standard Spectra Autotune was changed from 25 1020. However 25 still comes as the default value in the software, so if you're experiencing peak splitting lower the maximum repeller to 20. The absolute abundance of 69 is typically 200,000 counts, the relative abundance of 219 is usually between 20-80%, and the relative abundance of 502 is typically around 2%. ‘This autotune should be used when analyzing medium to high level samples in average to dirty matrices. The linear dynamic range given by this tune will be about 5 orders of magnitude. Quick Tune ‘Quick Tune adjusts the EM voltage and the mass assignment only. It does not alter ion ratios. Quick Tune will use the lens parameters of the current autotune. However, it will always set the detector voltage to the Standard Spectra Autotune value. Target Tune ‘Target tunes are available on Mustang III to tune for BFB and DFTPP. The new target tunes incorporate a feature called Dynamic Lens Ramping. From looking at the autotunes for Max Sensitivity and Standard Spectra you can tell that the amount of high mass versus low mass differs dramatically depending on where you set the entrance lens offset. Accordingly, Dynamic Lens ‘Ramping ramps the entrance lens offset to give high low-mass abundance when it's scanning Jow mass and then it raises the entrance lens offset value to give good high-mass abundance when scanning the high mass. 18‘Set Tune Targets... Save Tune Targets... Load Tune Targets... Set Maximum Repelle Set Maximum Jon Focus... Set Peak Width Target... figure 3 If your target tune fails to pass the BFB or DFTPP criteria when you acquire either one, you can adjust the tune targets. Select Set Tune Targets from the menu shown in figure 3. The Tune Targets dialog box appears see below in figure 4. Depending on which ion is out of range and whether its low or high adjust the corresponding PFTBA ion (j.. if 50 is out of range adjust mass 69). If the ion is low raise its target and lower the other targets. If the ion is too high do the converse operation: lower its target and raise the others. TuneMS —AcquireData DataAnalysis file Tune Execute Calibrate RampParam ied Mass 131 target in bz] Mass 219 target Er Mass 502 target in %: 08 19In addition to changing the target values, several other “maneuvers” can be done, depending on the needs and skill level of your customer. Dynamic Lens Ramping is a new feature and doesn't have a “track record" with respect to running EPA performance samples. Therefore, you may want to disable the dynamic lens ramping feature. Refer to figure 5 below. To disable the dynamic ramp just click on that choice. “File_Tune_Exeewte Calibrate IS amp ion Fecas Ramp Ent Lone ‘amp Ent Lene Oset Ramo way ‘iene Dynamic Lone Ramp Dyan Lens Remng Meanie Senenviy figure 5, This will disable the ramping feature. Then you will need to select Edit Dynamic Lens Ramping. The dialog box shown in figure 6 will appear. Set the entrance lens offset to whatever value you feel is appropriate. Remember, in order for the instrument to not ramp they will have to all be set to the same value. Then save the values to a tune file and make sure that the appropriate tune is selected when a method is run, This will only disable the ramping feature until the next target tune is run; it is not possible to permanently disable the dynamic lens ramping. 0.4 jm). No effective loss of efficiency for thinner film columns was reported. Nevertheless, any loss of chromatographic resolution can easily be compensated for by inereasing the length of the column. On the other hand, one of the benefits derived from the vacuum outlet connection is increased analysis speed. Bernier® demonstrated an improvement of analysis speed by a factor of 2 using a short capillary column with an FID under vacuum outlet conditions with a 6% loss in resolution. Another significant benefit of the MSD is remarkable reten- tion time reproducibility, an important feature used in “target compound analysis.” Although the primary factors in the achievement of excellent retention time reproducibility are the use of a GC with precise ‘temperature control, fused silica columns, and sample injection technique, the lack of undesir- able effects due to the capillary direct interface are also impor- tant. Examples of good retention time reproducibility will be shown below. The MSD is a true universal response detector. It responds to all classes and types of com- pounds (e.g. hydrocarbons, halocarbons, phosphorous- and nitrogen-containing compounds, ‘gases, and inorganies), including ‘those to which an FID does not respond. Virtually any com- pound which will survive gas chromatography and has a molecular weight below 700 amu (the upper limit for the HP 5972A) can be identified. As an example, the mass spectrum of hexabromobenzene (hereafter abbreviated as HBB; molecular weight = 545.49 for the isomer containing only the Br-79 iso- tope) is shown in Figure 7. The top window of Figure 7 (460-570 armu) shows the peak cluster representing the molecu- lar ions with six bromine sub- stituents and 6 carbon atoms. Knowing a little bit about mass spectral interpretation, you can very easily identify this com- pound even without a library search. This is a major advan- tage of the HP 5972A which produces “classical” spectra. The HBB mass spectrum shown was acquired in the scan mode of the HP 5972A using a mass range of 50-610 amu.2200000 | Ce 1200000 cholesterol 1000000 000004 I il i\ i a) WI A Figure §. Total Ion Chromatogram of Cholestane (90 ng) and Cholesterol asng). GC conditions: 30m x 0.25mm HP-5 Crosslinked 5% Phenyl Methyl Silicone Gum capillary column, 45 emisec He linear velocity, temperature ramp—1 min @ 70°, 25/min. to320',5 min @ 320", injector = 250", transfer line = 280°, Solvent: iso-octame, 1 iL splitiess injection. SIM mode amount of time (user specified) measuring abundances of a small number of selected masses only. These masses are chosen to be very specific for each com- pound in question. The most ‘unique and significant ion of the ‘mass spectrum is chosen as the “quant ion” and is typically Not only is the MSD considered auniversal detector, it becomes a selective detector by using the HP 5972A in the Selected Ion Monitoring (SIM) mode of opera- tion. With the SIM mode, the ‘mass analyzer spends a specific ratioed against two other “qualifier ions”. These ratios and the ion’s retention times are matched with a known com- pound to confirm the identity of the compound. This procedure is legally defensible in a court of law and can be used to detect trace amounts of a target com- pound in a complex sample matrix. The use of the SIM mode also enhances the sensitiv- ity of the MSD by 5 to 100 times compared to operation in the sean mode. In scan mode one may detect compounds in the Jow-picogram range while in SIM mode detection limits are typically in the high-femtogram to mid-femtogram range. Sen- sitivity and selectivity are the big bonuses for operation in SIM mode, The SIM mode of operation is also the preferred way to quan- titate samples because it gives more reproducible quantitation of peak areas than in the scan mode. Quantitation is performed by measuring the peak area of the most unique and significant ion of the mass spectrum (the quant ion), Measuring a ‘unique ion helps insure that background and noise is not included in the quantitation value. This differs from quanti- tation done with a typical GC detector where the total peak area is measured. A plot of the peak shapes of ion 551.55 (the most abundant unique ion) for five consecutive injections of HBB, in the sean mode, is shown in Figure 8. The relative standard deviation of‘Abundance Average of 13.964 to 14,004 min.? CHOLEST?.D (+,*) 8000 6000 a 5000 | sooo 1 | 275. 3000 4 20004 1000 ° ! njzn-> #0 60 80100 120 140 160 180 200 220 240 260 260 300 320 340 360 360 Figure 6. Mass spectrum of Cholesterol (16 ng). Ratio of 384/386 = 0.01. Ratio of 368/386 = 0.42. MSD conditions: sean mode, 35-400 amu scan range, threshold = 100 counts, a/d samples = 4, seans/second = 20. the peak areas for ion 551.55 is Day-to-day reproducibility and _various and easy-to-use tune 4.23%. When the peak shapes of stability are important features procedures. (A tune is a simple ion 551.55 are plotted for five of an ideal detector. With the automated procedure that sets consecutive injections of HBB in MSD these features allow for _ the parameters of the instru- the SIM mode (Figure 10), the the construction of a user- ment to meet certain perfor- relative standard deviation goes created database (data obtained mance criteria). It is this down to 1.52%. Also, note that today can be compared with reproducibility and stability figures 8 and 10 are examples _data collected months previ- that make the HP 5972A so of the excellent retention time _ ously). Also, data from the user's popular with customers doing reproducibility achievable with system can be easily compared _ target compound analysis for the HP 5972A when coupled with data obtained on other MS __a living. In these analyses, with the HP 5890 Series II GC. __ systems. Recalibration or tuning any time the operator has to The five consecutive HBB injec- of the system, as might be nee- _retune or recalibrate his/her tions easily fall within a one essary for quantitation, is less _ instrument, it means a loss second time window. frequent with the HP 59724’s —_in revenue.‘Abundance ‘Sean 336 (12.734 min): HBB.D (#) 70000 552 50000! Iss0 300004 20000} | [eel | lars. | 546. Ll Lae 497507 saa . Lil ajerc> 465 430 475 480 485 490 495 500 505 510 515 520 $25 530 535 540 545 580 595 560 Rbunaance Scan 336 (12.730 win]? HBB-D(*) 700004 2 | | an 1 ll ‘sse i 552 60000 4 50000 4 ass 40000 72 300004 us an 20000 | " 276 ni p25 356 ger 516 150 260 250 ~«4300,~=St«C«SSaOSSCBOSSC*«OSSC« SO Figure 7. Bottom window: Mass spectrum of Hexabromobenzene. Top window: detailed view of molecular ion ‘mass range. ‘MSD conditions: 50-610 amu sean range, threshold = 100, a/d samples = 4, seans/second 3. Conclusion References The MSD is the best general GC 1. McNair, H.M.; Bonelli, E.J.; 4. Cramers, C. A.; Scherpenzeel, detector available today. It is Basic Gas Chromatography, G.d; Leclereg, P. A. . inert to the analysis, offers day- Consolidated Printers: Chromatog. 208, (1981) 207. to-day and long-term stability, Berkeley, CA, 1969. responds well to all compounds, 5. Bernier, U. R.; Rossi, S.; Yost, provides absolute compound —_—, Buffington, R; Wilson, M.K.;_R. A., “Short Capillary Col- identification, and has the capa- Detectors for Gas Chromatog- umn GC/FID under Vacuum. bility of performing reproducible raphy—A Practical Primer, Outlet Conditions and Its quantitative analysis. With Hewlett-Packard Co., Relevance to GC/MS,” June these capabilities and the appli- Avondale, PA, 1987. 1990, American Society of cation software's ease of use, ‘Mass Spectrometrists isn't it time to take a look at the _ 8. Watson, J. T., Introduction to (MP 38). HP 5972A MSD? Mass Spectrometry, Raven Press: New York, 1985; p 130.eT 9 Figure 8. Extracted Fon aoudence yon 200-38 (g9i-28 to g92-20): msc o Ceesnieaccet incest el ion 385038 GE38 $5 395038)! mansenes’ Ghromatograms of jon $51.5 of Ton S5uc38 (S0ic3s fo 988035)! mmnscnes:D : 000 Ton sivas (ssicas to 982038): wapssroe.D Standard Deviation of peal areas Eon S52038 (S50c3s @ $58:35): onssnos-3 Stas. GC conditions: 30m x 0.5mm HP-5 5000 Grosslinked 5% Phenyl Methyl Siltcone Gum capillary column, 45 cmitec He linear velocity, temperature ramp—I min @ 70°, '30°/min. to 200", 20°/min. to 240°, 5*/min, to 300°, injector = 280°, transfer line = 280°, Solvent: iso- octane, 1 uL splitless injection. MSD conditions: 50-610 amu scan range, threshold = 100, a/d samples = 4, scans/second = 1.3. ie name Tien 387,70] Ton SBT.SS | KIGT.TORET.ES | lon 257,80 | GIST BRBT.ES HESSCNOTD, 72.72 | e211 | 1032232 [37.61 1458661 [144.20 HBESCNOZ.D_ 72:72 [401791 | 1067634_| 37.64 1540194 144.28 HBESCNO3.D_ 12.72 | 411960 | 1098078 | 37.52 1618660. 147.41 HBSSCNOS.D_ 12.72 | 4092541131206 | 36.18 1617725, 143.01 HBESCNOS.D_ 12.72 | 433651 | 1145657 _|___37.87 1670862 145.85 Average [1a72 | aos0rs | Tosaeet_|___ 37.38 1587200 _| 144.55 Sid dev. % [oor 4.97 423 1.80 455 116 Figure 9. Scan data from Figure 8 plotted in a custom reports package. 10Figure 10. Extracted Jon Chromatograms of ion 551.55 of Hexabromobenzene, SIM mode standard deviation of peak areas = 1.52%. GC conditions: 30m x 0.25mm HP.5 Abundance on on ss1.5s 35338 (ssn (351.25 to 552.25) {35125 to $52.25) (35125 te 552.25) 38 to $52.25) (551138 te $52.28) uapsrx02-p MBBSINOS..D Crosslinked 5% Phenyl Methy] Silicone Gum capillary column, ‘90000 45 omisec He linear velocity, temperature ramp—1 min © 70°, ‘85000 ‘30°Mmin. to 200°, 20min. to 240°, ‘5"/min.to 300°, injector = 280°, 0000 transfer line = 280°, Solvent: iso- ‘octane, 1 UL splitless injection. 78000 ‘MSD conditions SIM mode, ions 70000 351.85, 991.70, 281.80, 75 msec dwell time, eyele rate = 3.55/sec. 65000. 60000 30000 15000 eo a7 ~Caareo «Cabo Fig name | lnection Time | AT [lon 301-70] ton 651.56 | ESOLTORST.ES | lon 25160 | GOS1-BRSI ES HBBSIMOTO | 16:61 72.72 | 694391 | 1923282 38.08 "2630307 155.23, HBBSIMO2.0 | 17:07 312.72 | -705190_| "1837007 38.39 72867402, 156.09. HBBSIMO3.0 | 17:33 12.71 | 702548 |_1829936. 38.39 2871601, 156.92 HaBsIMOs.0 | 17:59, 12.71_| 715675 | 1866942 38.33 2973907 756.62 HEBSIMOS.O | 18:25 12.71 | 727195 | 1889696 | 98.48 2982720, 187.84 13:72_| 708000 _| TBST. E30 2ESBTSS. T5654 0.03 [1.79 [1.82 0.39, 2.05, 0.62 Figure 11. SIM data from Figure 10 plotted in a custom reports package. iG HEWLETT PACKARD Hewlett-Packard shall not be liable {for errors contained herein or for incidental or consequential damages in connection with the farnishing, performance or use of this material. Information, descriptions and speci fications in this publication are sub- Ject to change without notice. (23) 5001-6005E Printed in the U.S.A. (11/92)HEWLETT PACKARD Sensitivity of the HP 5972A MSD Patrick D. Perkins, Ph.D. MS Application Brief The sensitivity of a GC/MS as shown here. What follows here system results from careful is not a change in the specifica- attention to and maintenance of _ tions for the HP 5972A MSD. all parts of the analysis: sample HP will guarantee that an preparation, injection technique, HP 5972A MSD will meet the liner and cleanliness of the sensitivity levels in the specifica injection port liner, column and tion sheet, publication number column bleed, how the MSis (23) 5091-5562E tuned, state of cleanliness of the ion source, and a host of other A GC/MS system comprised of factors. (For a detailed discus- an HP 7673 ALS, 5890 Series II sion of some of the factors affect- GC, and HP 5972 MSD was ing sensitivity, see a related _ outfitted with the following parts application note.") By paying _ contained in the shipping kit for attention to these factors, one the HP 5972A. To obtain the low may obtain sensitivities sub- _ sensitivities illustrated here, stantially greater than what is it is essential that parts with reported in the specifications for inertness and low bleed charac- the HP 5972A MSD. Note: the _ teristics equivalent to these specifications listed in the speci- parts be used in the system: fications sheet for the HP 5972A are values which should be Table 1. Parts for GCMS system obtainable over the lifetime of the instrument. If the HP 59724 is well maintained, it may sub- stantially exceed the EI scan or EISIM sensitivity specifications, or septum (pack of 25) ‘30m x 025mm 0.254 HP-5 clu HP 5972A MSD Mass spectrometer MS 92-11 ‘The system was tuned while set to the temperatures and pres- sures given in the acquisition parameters table (Table 2), with the exception that the GC oven was set to 250° C instead of the “start-of-run” temperature of 70° C. The mass peak width target for the tuning was set to 0.65 amu using a menu item in the Manual Tuning program. (This was done only the first time the MSD was tuned.) Then the system was tuned automati- cally using the “maximum. sensitivity autotune” in the HP G1034C MS ChemStation (DOS series) software. A similar 5101-3 Pesticide grade injection portiner with deactivated glass wool py 5062-587 1gs-438tune exists in the MS Chem- System (HP-UX) software (HP 59944B version B.06, and HP 59944C version C.01). Data were acquired using the parameters in Table 2. ‘The data are shown in Figure 1. For this GC/MS instrument, the RMS signal/noise for mass 283.8 of hexachlorobenzene is 127, approximately 13 times better than the specification. The background-corrected average spectrum from this injection yields excellent PBM (Proba- bility Based Matching) library search results (Table 3, match quality = 96 when searched against the NIST library, 74,828 spectra). Note that the table contains much additional infor- mation about the search. For this search, three different hexachlorobenzene spectra matched the unknown with high confidence; the reference num- bers are shown. Despite the presence of “noise” masses in the spectrum, the search proce- dure considers the unknown spectrum relatively uncontami- nated (low values for “Con”). In the last column of the table are shown the match qualities for a “eross-correlation” comparison, which uses (mass * abundance) as the means of comparison ‘Again, the match qualities are very high, attesting to the high quality of the unknown spectrum, Table 2. Instrument parameters for scan acquisition rameter Value Injection por temperature 250" MSD interface temperature 700° (ven temperature program 10° @ 15 minutes, 25/nin to 280", hold3 minutes Inlet pressure 1S psig Pressure program none (constant pressure} Sample 10pa/d hexachlorebenzene Solvent isooctane Injecton volume tL Purge on tine 15minutes spives injection) Sean range 50-300 amu ND samples 23 (ca. 17 scanslsecond) Threshold ° EM seting + S00Vcelative tothe tne Aeundance on 263.90 (203,50 to 204.10) Hcoi0Rs.0 wml ¢ biesthaaeremapen tate nfeientendond bitetapedee maven quatity © 96 Mist Library (74,828 spectra) “ballin 2) |. Extracted ion chromatogram for mass 283.8 and background ‘corrected spectrum for a 10 pg splitless injection of hexachlorobenzene.‘Table. Library search results for 10 pg hexachlorobenzene | PBM Search of irary DATABASEWBS7SK.L Name Monit ual 1 Benzene, hexachloro 72 cach, % 2. Benzene, exachloro mee cet * 3 Benzene, hexachoro- mm ek * 4 13-0yclopentadiene, 123,4-tetrachoro mm ctl a 5. Selenol(32-]Ibenzoselenophene 286 CyHSe, 2 8 Cyclobutene,12-dedor03-bisdiehlo me GHC o __Prob cast Rel KK Fag ton aw xcone “6 coone7e1 eS 8 . 6 & a2t ee a a ee] a 7 88 om 967 3 wren gst 7 =. 7 nas ee en o on 8 8 ez 5 “2 ocoigens ae HD 8 owe 6m oss0e46.7 © e008 TTT 1 o 8 8 es ot El teenie te exasilt VR i es eee een TS El SIM mode, the HP 59724 Poraneter Yair MSD was tuned as before. Data Instn port temperature 20 were acquired using the param- | yspinrfcetenpereure 280" fers in Tables Oven temperture prom 70° @15 minstes, 25/in to 260, hold minutes inet pressure esa Pressure progam sone (constant pressure) Sample 200 gph hevachoroberzone Sohent isooctane Injection volume tt Purge ontime 1Smints pies injection) SM mass 2e38amu Dnt tine soomsec Low mass resolution ves Esoring +400 ate tote tune(a eet (EB PACKARD The data in Figure 2 show that this HP 5972A MSD has excel- lent sensitivity under these conditions, yielding detection limits for this compound in the mid-femtogram range. In conclusion, the HP 59724 MSD will produce usable spectra in full sean mode on compounds in the mid- to low- picogram range, and it ean detect substances in the high- to mid-femtogram range in SIM mode. In addition, the use of electronic pressure control (EPC) will allow injection of larger sample volumes, further reducing the detection limits. However, in order to achieve these low sensitivities, the parts in the GC/MS system, including injection port liners and column, must be selected for maximum inertness and mini- mum background. References 1, Doherty, Linda; “Optimizing splitless injection on your GC for high performance MS analysis,” publication number (23) 5091-4587E (9/92). ts stgna/notee = 0 | Figure 2. Ton chromatogram for mass 283.8 of hexachlorobenzene, SIM. ‘mode, 200 fg injected in splitless mod. Hewlett-Packard shall not be liable for errors contained herein or for incidental or consequential damages in connection with the furnishing, performance or use of this material. Information, descriptions and spec fications in this publication are sub- Ject to change without notice. (23) 5091-62378 Printed in the USA. (11/92)HEWLETT PACKARD Optimizing splitless injections on your GC for high performance MS analysis Linda Doherty GC/MS Application Note Trace level GC/MS analysis requires a system that is per- forming at its best. Without a properly optimized GC, the mass spectrometer may not give the sensitivity expected. In other words, if the sample does not make it from the injection port to the ion source, the detec- tor will not detect a signal. Also, if the chemical noise from the GC is too high, the signal-to- noise ratio will be reduced. This note is a “how-to” guide for improving the GC performance. This will, in many instances, improve the overall performance ofa GC/MS system. This guide is specific for the HP 5890 Series II GC used with any HP mass spectrometer (5970, 5971 or MS Engine (5989)]. To upgrade an existing HP 5890 to a Series IT order P/N 19230T or U depending on the serial number of the GC. The T upgrade is for more recent GCs, serial numbers 2908Axxcxxx to 2931Axcccxx (Europe: 2913G:000n to 2921Gxxx0). ‘The U upgrade is for those GCs with part numbers prior to 2908Axxxxx (Europe: 2913Gx000.). To find the serial number, open the oven door and look on the lower lip. It will be on a sticker right in front. Con- tact your HP salesperson for upgrade information. HP 5970B MSD HP 5971A MSD HP 5989A MS Engine HP MS ChemSystem HP MS ChemStation (DOS Series) GC/MS 92-3 Supplies In order to improve the perform. ance of the system, there are some supplies that should be on hand. These supplies are recom- mended and each by itself may not improve instrumental per- formance, but when installed with the other parts will give the best results. Many of the supplies which will be refer- enced have changed over the past few years. Your lab supply may not contain the most recent product. Updated versions of consumables should be purchased.‘The carrier gas line The GC carrier gas should be 99,999% helium (called 5 9's helium). Less pure grades of He are available and can contain impurities that can damage the GC column (e.g., oxygen) and contribute to the chemical noise background. Clean 1/8" copper tubing should be used with high quality carrier gas. Refrigera- tion grade 1/8" copper tubing is pre-cleaned. Tubing can be cleaned by running solvents (methanol, ethyl acetate, hex- ane) through it in a water aspirator vacuum set-up. The use of chlorinated solvents is not recommended due to possible long term contamination of flow lines and controllers." Even with a high purity gas there may be trace water, oxygen and hydro- carbons. Putting a trap in the carrier line will eliminate these contaminants (see Figure 1). An indicating trap will remind you when to change it. However, most indicating traps have low capacity and may have to be replaced every 1-3 months. By using high purity helium, they will last longer. OWO# Vale Main Gas Toston oan — Oa sso } € ‘upohy Figure 1. The supplies needed for the car- rier gas line are: + 99.99% He: Gas supplier ‘+ Clean copper tubing (50 ft): HP PIN 5180-4196 + Indicating moisture trap: HP PIN 3150-0532 * Indicating oxygen trap: HP P/N 3150-0528 Splitless inlet consumables The split/splitless inlet (Figure 2), has many consumable parts that should be kept on hand. Many of these consumables, such as liners (5), come in a variety of designs (Appendix A). The proper liner to use is very dependent on the application. For trace level analysis the single tapered, deactivated liner is recommended. The Viton O-ring (4) holding the liner in place, should be replaced peri- odically to reduce the chance of General gas plumbing assembly leaking. The seal and the washer in the bottom of the injection port (8, 9) should be replaced whenever bottom nut is removed. The recommended seal is gold plated to reduce metal catalyzed thermal degradation. Septa (2) should be replaced quite frequently, at least every 100 injections. The low bleed, red septa should be used. Keep- ing a beaker of septa in an oven at 250°C at all times will elimi- nate the need to condition the septum once it is in place. A Merlin Microseal” is highly recommended over conventional septa, The microseal eliminates the need for septa and lasts for tens of thousands of injections without leaking. It is most appropriate with the HP 7673 autosampler and only works with untapered, blunt tip syringes. "Another commonly used cleaning technique isto heat the copper tubing with a Bunsen burner or propane torch while helium is flowing through the tubing. This is done after connecting the tubing to the helium supply but before connecting it to the GC. This process bakes off all the volatile contaminants. Safety precautions should be taken if this procedure is done,A final recommendation is to SD © serene ator ‘upgrade the manually controlled ran Mrosea splitless injection port to elec- tronic pressure control (EPC) 2 Septum ony with sepumretineroit) | Electronic control will give the Ss — best reproducibility in retention 21 spss ise aden with ain aa aera "to | time and area counts and allow for complete transfer of larger S 6 berseats volume injections (up to 5 41) ‘ton O-ing for hightemperature onto the column. Larger volume tna 350°) injections may result in more inlet maintenance, especially | 5. seelinertable Appendix A | with dirty samples. ‘The list of splitless inlet consumables are: ‘+ Molded Septa (11mm, red, ee | 25/pk): HP PIN 6181-3383 OR * Merlin Microseal” starter kit: HP PN 5181-8816 + Liner, single taper, deacti- vated, no glass wool: HP PIN 5181-3316 * Viton O-ring (12/pk): HP P/N 5180-4182 Retaining nut se | Washer * Gold plated seal: HP PIN. 18740-20885 ee * Washer (to go with seal): | HPPIN 5160-5869 * Blunt tipped syringe: Lower insulation HP P/N 9301-0713 Lower insulation Lower insulation cover Column ferrule Column nt Figure 2. Splivsplitless inlet assemblyColumn consumables The choice of column is once again dependent on the applica- tion. For trace level, high sensi- tivity applications, a column with a thin film and low bleed is best. A 30 meter, 0.25 mm ID, 0.25 mm film, 5% phenyl-95% methyl silicone column is a ver- satile column that can be used for many applications. The col- ‘umn should have specifications for low column bleed. These special columns cost more, but will give better results. The proper column nut and ferrule combination are critical for a leak tight seal. Newer column nuts may not be compatible with all ferrules. The proper ferrule will be dependent on column diameter and is specified here. The ferrule should only be slightly larger than the column outer diameter. The use of 100% graphite ferrules is not recom- mended as they are easily over tightened causing graphite to extrude into the injection port. This will be apparent when dis- assembling the injection port. If there are pieces of graphite in the bottom of the injection port the ferrule(s) was (were) over- tightened. The presence of ‘graphite in a hot injection port can cause thermally labile com- pounds to degrade. It can also effect the chromatography and cause tailing. Thus 10% graph- ite, 90% Vespel ferrules are highly recommended. Vespel ferrules will shrink as they are heated. Conditioning them for 4 hours in a 250°C oven will pre-shrink them before use. Alternatively, the column nuts can be retightened after heating the appropriate zone. ‘The column, column nut and ferrules supplies are + 30 m column, 0.25 mm ID, 0.25 mm, low bleed: HP P/N 19091S-433 * Column nuts (wrench tighten only) 2/pk: HP P/N 18740-20870 © ferrules for 0.2 mm ID col- umns, 10/p! HP PIN 5062-3516 * ferrules for 0.25 mm ID col- umns, 10/pk: HPPIN 5181-3323 © ferrules for 0.32 mm ID col- umns, 10/pk: HP PIN 5062-3514 A sharp column cutting tool is needed for making clean cuts. ‘The sapphire square edge pens (Restek and Supelco) or ceramic scoring wafers are desirable. ‘The diamond point pens are harder to use. An X-ACTO™ or Swiss Army knife is not a col- ‘umn eutting tool. A 10x magni- fier should be used to assure that the cut is clean and no col- umn shards are lodged inside the column, Interfacing the column to the MS The column is connected to the mass spectrometer through an interface that is sealed with a column nut and ferrule. The ferrule used is dependent on the column used. A 100% graphite ferrule should never be used? The ferrules required are 15% graphite, 85% Vespel. The col- ‘umn nut listed is brass; stain- less steel nuts should never be substituted. Stainless nuts may damage the threads on the interface. Damaged threads cause air leaks and the entire interface has to be replaced. Similar to the injection port, pieces of graphite may extrude into the interface and contaminate the MS.‘The MS interface supplies are: * Column nut: HP PIN 05988-20066 * ferrules for 0.2 and 0.25 mm ID columns, 10/pk: HP P/N 5062-3508 * ferrules for 0.32 mm ID col- umns, 10/pk: HP P/N 5062-3506 Installation of consumables ‘This section assumes that there is an existing GC in the labora- tory. If this is a new GC, many of these steps will be completed by the Customer Engineer dur- ing installation. Before begin- ning the installation please read this section carefully. Have on hand the GC site prep manual, the GC operating manual, the GC reference manual and the MS hardware manual; they will be referenced frequently. ‘The manuals needed are: * GC site prep manual: HP PIN 05890-90280 * GC operating manual: HP PIN 05890-90260 * GC reference manual: HP PN 05890-90270 + MS hardware manual (5971): HP PIN 05971-90019 + MS hardware manual (5970) HP PIN 05970-90049 ‘+ MS hardware manual (5989) HP PIN 05989-90009 ‘When all of the consumable supplies, previously mentioned, are received, a proper preventa- tive maintenance (PM) can be completed. To begin a PM it is necessary for the GC zones to be cooled (oven, injector, MS inter- face). The benchtop MS systems have to be vented. Please refer to the HP 5989, 5971 or 5970 MS Hardware Manual for vent- ing instructions. Installation of gas supplies Following the directions, start- ing on page 1-8 in the GC Site prep/installation manual, install the gas line supplies. Care should be taken in making the swagelok connections. The glass indicating traps can be easily broken if too much stress is placed on the connection during tightening. Leak check all con- nections with a helium leak detector. (No Snoop™ please!) Make sure that all the lines are purged with helium before con- necting them to the GC. Installation of splitless injector supplies Before handling any of the injec- tion port supplies wash hands and/or wear gloves. Oils on the hands will be transferred to these parts and become back- ground in the system requiring extra bakeout time. Washing the hands is especially impor- tant after eating. Following the instructions in the GC operating manual (pages 2-4, 2-5), remove the septum nut, septum, and liner. Discard the septum, liner and liner O-ring. Open the oven door, loosen the 1/16” column nut and remove the column and nut. Remove the lower insula- tion cover and insulation (Fig- ure 2, #11, 12). If the lower insu- lation cover was not in place, find it, because this piece improves the inlet temperature profile.With a /2" wrench remove the reducing nut (Figure 2, #10). Due to heat cycling of the GC, the reducing nut will be very tight. Remove the washer and the seal (Figure 1, #8, 9) and discard. Place a new washer in the reducing nut and a new seal (fat side up, with groove). Hand tighten the reducing nut back into place and then wrench tighten until very tight. Replace the lower insulation cover. Insert a new liner and O-ring. The single taper liners are installed with the taper down, closer to the gold seal. Hand tighten the weldment (Figure 2, #3). Add the Merlin Microseal™, or proper pre- conditioned septum and septum. nut. The molded septum is installed with the hole up. Fol- low the directions supplied with the Merlin Microseal™ to insure proper installation. Wrench tighten the weldment and sep- tum nut with the septum nut wrench. Tighten the green sep- tum nut until the C-ring lifts off the top of it. At this point the inlet should be leak checked. Follow the direc- tions in the GC reference manual (pages 8-9 through 8-1). Column installation Working with fused silica col- umns may be dangerous. Wear proper eye protection. Inspect, the column for damage or break- age. Unweave some of the col- ‘umn from its basket to make it easier to work with. Cut a small amount of column from each end. Push a septum onto the injector end of the column about 10 em, Put the column nut and appropriate ferrule on the col- ‘umn, Cut 5-10 em off the injee- tor end of the column. Check the cut with a 10x magnifier, the cut should be straight, not jagged. If the cut is jagged, try again. ‘Mark the proper column posi- tion with the septum (Figure 3). The septum will hold the col- umn nut and ferrule in place. Place the column on the column hanger. Insert the column nut into the injector reducing nut and finger tighten. Wrench tighten the column nut. The column should not move. Care- fully slide the septum down, away from the nut without dis- turbing the column positioning. The septum can be left in place if desired, Open the total flow controller. Dial in the appropriate helium head pressure and set the split vent and septum purge flows (Table 1). The flow out of the split vent should be ~50 ml/min and the septum purge vent flow should be in the range of 0.5-3 ml/min. (For electronic pressure controlled systems this flow is fixed.) Place the detector end of the column into a beaker of acetone or water and check for bubbles to show helium flow. Heat the injection port. When the injection port reaches tem- perature, retighten the column nut, it may have loosened.Column Hanger Postion itary SplivSpiiess Capiliry niet al — tupaay | Catone | Fe | | — serum | — eet Figure 9. Proper installation of capillary columns in SplivSplitiess inlet. Check once again for column flow. Remove the end of the col- umn from the beaker and close the oven door. Condition the column by slowly (5°C/min) ramping it to its maximum operating temperature. Leave it at that temperature for least 2 hours, overnight is preferable. (The maximum operating temperature for an HP-5 column is 325°C.) Cool the oven to ambient and insert the interface nut and ferrule onto the column. Cut off 5-10 em more of the column. Properly insert the column into the inter- face by following the directions in the MS hardware manual. Hand tighten the interface nut and then wrench tighten the nut. The nut should be tight- ened only until you hear 2 squeaks. This is a firm seal. Pump down the benchtop MS systems as directed by the MS manual. Keep the oven at ambi- ent temperature until the source is hot. Check the interface con- nection after the interface is heated. The nut may need tightening.Table 1. Approximate head pressures and flowrates for a manual splitless inlet at ambient temperature. EPC inlet initial pressures should be set ~1 pai lower for the s same flow rates, because the pressure sensors and flow lines are different. Column Diameter Length Head Pressure UnearVelociy Column Flow ‘cm (rete ‘os ‘embee) ‘limi 02 2 2 x os % 2 x 0s 0 x» » 08 2s x» 8 » 08 os 0 5 2 19 03 oly ames * 0 0 138 ox 0 % x 138, Tips for better method The proper injection port te ature is needed to volatilize erformance Seal ia high boiling point compounds Numerous splitless parameters without thermally degrading need to be optimized for the best splitless injection. The GC refer- ence manual (pages 6-8 through 6-23) gives a thorough descrip- tion of the splivsplitless capil- lary inlet parameters. Table 2 summarizes them. ‘Table 2. Splitless parameters Injection port temperature Liner design Spltess vaWve time lum tow other compounds. Normally, the inlet temperature is a compro- mise between these two factors. A good starting point is 250°C. Sample volume Solvent Injection spees | ‘Sample vlaityLiner design is one of the most difficult choices simply because of the variety of liners available. ‘The features that are most important in a liner are the vol- ‘ume, whether it is deactivated or not and whether or not it contains deactivated glass wool. As a general choice for high sensitivity work, a 4 mm single tapered, deactivated liner with no glass wool is recommended. For large volume injections >2 ul, deactivated glass wool is necessary. For dirty samples deactivated glass wool helps to keep the non-volatiles from get- ting to the column, but too much deactivated glass wool can greatly decrease sensitivity and increase adsorption of polar compounds. Often, the most appropriate liner must be deter- mined through experimentation. Please note: removing and/or breaking deactivated glass wool creates active sites Splitless valve time is critical The time has to be long enough to assure that all of the injected sample reaches the column. A textbook splitless injection has the liner volume swept at least two times. A 4 mm liner has an approximate volume of 1 ml. With a GC/MS flowrate of 1 ml/min a two minute splitless injection would be necessary. ‘This long splitless time is not ‘common because the flow of the carrier gas is usually much higher than 1 ml/min at the initial oven temperature. This high flow is necessary because conventional splitless inlets are pressure regulated (constant pressure, regardless of oven temperature) and not flow regu- lated (changing pressure with oven temperature). Initially, a higher than optimal flow is set 30 that the flow does not go to zero at high temperature. Thus, a typical splitless or purge off time is only 1 to 1.5 minutes. A high initial column head pres- sure during the injection is also favorable for transfering all of the sample onto the column. As the injected volume is flash vaporized, the required expan- sion volume for the solvent is greatly increased, (Solvent choice also effects expansion volume.) With higher pressures the volume is reduced (P,V, P,V,) and the entire injected volume moves to the column. The higher pressure also decreases the likelihood that highly volatile compounds will escape out the top of the injec tion port through the septum purge vent (Figures 4 and 5). Finally, it has been found that fast injections tend to give the ‘most reproducible and non- diseriminating results.‘Soptu Septum Purge Vert = Tae Cartier Gas In Inlet Purge (Om) Low Init Pressure(Low Columa Flow |< =more volatile compound Cod 455 volatile compound Column Figure 4. A low initial inlet pressure causes loss of volatile compounds. Septum Carrer Gas In Septum Purge Vont — | High niet Pressure/High Column Flow more volatile compound 5 volatile compound Figure 5. With the correct inlet pressure, there is no loss of volatile compounds. 10 The initial oven temperature should be set to take advantage of the solvent effect. The solvent effect focuses the analytes on the head of the column. The ‘oven temperature should be set to 10-30°C below the boiling point of the solvent used (Table 3). The interface temperature (and MS source temperature for ‘the 5989) should be hot enough 50 as not to cause a cold spot and condense analytes. The analytes’ boiling points can be used as a guide. Alternatively, with benchtops, the interface can be set to the maximum oven temperature for the analysis. The default temperature is 280°C and should be optimized as part of method development.Table 8. Boiling and initial oven temperatures for common solvents, Boing tial oven Sowent pom '€)tenperaure Dietwiener Toto nForce = TOS Mativene corde 9101030 Corendieide 4 101035, Chlorerm 2stos0 ethan 6 sts An application to consider. . One possible way to improve a splitless injection is to use elec- tronic pressure control (EPC). Electronic pressure control of the splitless inlet allows for high pressure initially, followed by more typical GC/MS flowrates. ‘The flowrates are held constant as the oven temperature increases because the pressure is programmed. This transfers more of the sample onto the column and allows for increased injection volumes up to 5 ml. Figure 6 is a graphical represen- tation of the “pressure pulse” injection technique. Not only does electronic pressure pro- gramming (EPP) increase the amount injected, it decreases the run time. It also increases the chromatographic resolution by keeping the carrier gas flow constant and optimized (van Deemter’s equation). It is a technique that is worth investi- gating because it gives accurate control of the column flow. rtiexene Ethyl acetate Acetonitrile n-Heptane Octane Toluene 30psi SZ 3 7 wees 2 aun = nee = ws one I 7 OC Fae sion ; © z woo 3 wore ‘3hm x 0.25nm 1 column vacuum compensation on 5 0 8 m 6 wo Fun Time Figure 6. The “pressure pulse” injection technique with electronic pressure control (EPC). This technique allows for larger injections and inhibits the loss of volatile compounds out, of the septum purge vent. WLHEWLETT PACKARD @ Appendix A Capillary Inlet System Liners Information Sheet Selection of the proper glass liner is an important factor in obtaining optimal GC performance.* The liners available for use with HP models 5890, 5880, and S7XX gas chromatograph split/splitless ‘capillary inlets include both untreated and deactivated types. ‘The liners are described here and can be ordered through the Hewlett-Packard Chromatography Users Catalog, ‘Section I includes the undeac- tivated liners and one which is available with and without treat- ment. The remaining deactivated Jiners are described in section Il ‘A summary of configurations and applications for both types is given in section III. I. Untreated Liners Untreated liners are available for the following injection techniques: split, splitless, and capillary direct. ‘These liners are made of either borosilicate or quartz glass in the ‘configurations shown on this page. ‘Standard deactivation procedures can be used as needed with the unpacked liners. Amore detailed discussion of inlets and liners ean be found in the book "GC Inleto—An Introduction,” CHP part no, 8958-0468) ‘SplilSplidess Liver === [HP Part No. 19251-60540 This splitsplitiess liner is a general- purpose liner that can be used with either injection technique, and is recommended for fast split tions with the HP 7673 Automatic ‘Sampler. The liner is constructed of borosilicate glass and contains silanized glass wool packing, to ensure vaporization of the sample before it reaches the column entrance. The glass wool plug should always be used for split injections and is preferred for fast autoinjection, but it may be removed for some splitless applica tions if the samples are free of particulate matter. The liner has an internal diameter of 4mm and a nominal volume of 990 ul. Split Liners E =———s HP Part No, 18740-60840 [HP Part No. 18740-80190 ‘These liners are used for split mode operation and for slow manual or slow automatic injections. They are constructed of borosilicate glass, 4mm id, with a nozzle/cup mixing chamber. Liner 18740-60840 con- tains a small amount of column packing (10% OV-1 on 80/100 ‘Chromosorb-WHP) retained by silanized glass wool plugs. 3 Gas Chromatography September 1992 Splidess Liner SSS FHP Part No, 18740-50220 (untreated) and 5181-8818 (deactivated) This liner is useful for splitless mode of operation with slow injections, small (<0.5 wl) sample volumes, and higher-boiling solvent systems. It is constructed of quartz glass, ~2.0 mm id, with a nominal volume of 250 ul. As of January 1992, itis also avail able with the polysiloxane deactiv- ation described in section II for the tapered liners. Direct Liner Ee [HP Part No. 18740-60200 This liner provides a low-volume connection to other sample introduc- tion devices (headspace, purge and trap) or to large-bore capillary columns for direct injection. Itis constructed of borosilicate glass, ~1.5-mm id, and has a nominal volume of 140 yl. NOTE: The two narrow-bore liners (HP part no. 18740-80220 and 18740-80200) are similar in appear- ance, and care should be taken to avoid exchanging them in use. Ii. Deactivated Tapered Liners The three liners shown below were developed for improved performance in work with sensitive compounds,particularly for pesticide analyses. ‘They make use of surface deactiva- tion as well as liner geometry to provide greater inertness. Use of the gold-plated inlet seal (HP part ‘no. 18740-20885) in combination with these is recommended for further inertness in pesticide work. All three are made of borosilicate glass. This new design has a tapered neck either at the bottom (single taper) or at both ends (double taper). The nominal volume is similar to that of the straight 4 mm id split/splitless liner (HIP part no. 19251-60540). The single taper liner is available with or without a small plug of deactivated glass wool for splitless applications, and can be packed by the user after cleaning or for split injections. Columns should be installed as recommended in the HP 5890 Operating Manual, ~ 5mm past the end of the ferrule, so that the tip will be properly positioned in the taper. ‘These liners have been deactivated with a thin layer of cross-linked polysiloxane. They should be treated in much the same way as capillary columns with cross-linked stationary phases. They may be rinsed with organic solvents to 2008 remove sample residues, but more aggressive cleaning procedures (Strong acids, bases, oxidizing agents, etc.) should be avoided. Scratching the inner surface, as in removing or installing glass wool, should also be avoided. ‘The chromatograms below are for analysis of an endrin/DDT test mixture, using splitless injection with the single-taper deactivated liner (HP part no. 5062-3587) and gold seal (HP part no. 18740- 20885). ‘The figure on the left shows results for a clean system, with excellent recovery for both analyses and only traces of the degradation products endrin aldehyde, endrin ketone, DDE, and DDD. The chromatogram on the right corresponds to a system contaminated with use, where appearance of the product peaks can be used to evaluate perform- ance and indicate the need for liner replacement or other system ‘maintenance. Single Taper Liners HP Part No, 5062-3587 | HP PartNo. 5181-3316, These liners are used primarily for splitless operation, either with or without the small plug of silanized glass wool. Glass wool packing helps retain non-volatile conta nants and promote mixing for best reproducibility, but can also cause adsorption or decomposition of sensitive compounds, s0 the choice will depend on the application. For split injections, the small glass wool plug at the base of the liner may not provide adequate mixing for good reproducibility. For this application, an empty liner can be packed with a plug of deactivated lass wool positioned as in the straight 4 mm split/splitless liner (HP part no. 19251-60540). The liners have an internal diameter of 4mm, tapered to 0.8 mm at the lower end, and a nominal volume of 900 microliters. Double-Taper Liner oo HP Part No, SIBL-3315 ‘The double-taper liner is used for splitless mode operation. The internal diameter is 4 mm, tapered 10.0.8 mm at both ends, and the nominal volume is 800 ul. a a 2508 et voor 2006 soir || oor | ia set End Aah 1.064 / ein 000 J keove ooo 1008 lees — | sa00 ow ¥ ° 5 10 6 0 0 5 10 5 a ndkin and DDT, 100 ppb each in isooctane, 1-1 spliess injection, Column = PAS-1701 (HP part no. 19081801), 251m rin 80°, 30 deg/in to 190°C, ‘36 degimin to 250°, 032mm x025 um, helum cater ~¥2 i. 4 Inlet « 250°, Detector ECD) = 300°C‘en UOSBOU Bag = jE WOHUPUOUNUOSET IUD = 00208 OFaT ON a x coping | om ara ; a1a8 1619 ON Hea aH (@) (qB) 8 02Z08-OFLEI ‘ON H418d dH xX _ xX — ON. siquireay (9 Mung) ose a” | Someg? | Se ST SSTAe GOTOe OFLA ON Vd aH a x - - ow on | eosopouog | dno =z sour] yds, an 0F809-OF8T ‘ON 18d dH - |x = er vomeng | So | saa ON a ru (P) (P) oe x x sak ox | evening |S ©) woos x - |x - on | ea | enone [ones eo) a ‘qoury zoduj-oqnoq “oo Dee 1e19 ON ea aH x -— | X - Ce | | omy woury sodus-opsuyg ® wom 18i6 2909-ON Hd aH x HK] Kf HK] me] oat | ovmteien | ove tte | omy douyy aeduy ours sernts | mds | ewonds | ands | 2x? | pawanovoa] edgy een | m0 sqamy oma eonsstar enue pus AOS 19D) HOH UT aH TwonweanB yuo ‘sony | Stour] WroysAg JoTUT ATE] YdUD Jo AreMTMUNE “IT 15@ HEWLETT PACKARD Hewlett-Packard shall not be liable {for errors contained herein or for incidental or consequential damages in connection with the furnishing, performance or use of this material. (23) 5091-45878, Printed in the U.S.A. (9/92)HEWLETT PACKARD Improving the sensitivity of your GC/MS system with electronic pressure control Linda Doherty MS Application Brief Electronic pressure control (EPC) is a new way to set linear velocity, flow and head pressure in the splitless, purged packed and on-column injection ports. EPC precisely controls column head pressure greatly enhancing retention time reproducibility. EPC can be programmed to increase the column head pres- sure as the oven temperature increases. This allows for constant flow. In a constant pressure configuration, the flow through a column decreases as the oven temperature increases, ‘The decrease in flow is caused by an increase in gas (helium) viscosity and, at the same time, an increase in the fluidity of the ‘column phase. When the column head pressure is increased with the oven temperature, the ana- lytical run time is decreased. Compounds elute at lower tem- peratures and more samples can be analyzed in a day. Constant flow will also improve peak shape. Because the compounds come off the column more quickly, and at optimum linear velocity, broad chromatographic peaks are not as common. This will improve signal-to-noise determinations. Ina splitless injection the splitless valve time is eritical. The time has to be long enough to assure that all of the injected sample reaches the column. A. textbook splitless injection has the liner volume swept at least two times. A 4 mm liner has an approximate volume of 1 ml. With a GC/MS flowrate of 1 ml/min, a two minute splitless injection would be necessary. ‘This long splitless time is not HP 5971A MSD HP GC/MS ChemSystem HP MS ChemStation (DOS Series) ‘MS 92-5 common because the initial lin- ear velocity of the carrier gas is usually much higher than opti- mum. This is due to the design of the conventional splitless in- lets that are pressure regulated (constant pressure, regardless of oven temperature) and not flow regulated (changing pressure with oven temperature). So, a higher than optimal flow is set initially so that the flow does not go to zero at high tempera tures. In contrast, electronic pressure control of the splitless inlet allows for high pressure initially, (a pressure pulse) fol- lowed by more typical GC/MS flowrates that are held constant as the oven temperature increases because the pressure is programmed. Low initial pres- sures during the splitless time are not advisable and may cause loss of more volatile analytes.* # Note: Using the pressure pulse technique will eave your GC at a high pressure at the end of a run or sequence because the data system will reset all GC parameters tothe initial state. In a sequence the final run should be a standby method with standby pressures. This will reduce the comsumption of helium. For single runs this may be done manually, through the GC keypad. Alternatively, forthcoming application notes will address pre and post-run macros that can be added to a method to automati- cally set standby parameters at the end ofa run. Then, the analytical parameters will be downloaded before the news injection with a pre-run macro,Electronic pressure control was used to increase a splitless injec- tion volume size to 5 ul. Figure 1 shows the parameters used. Figure 2 is a graphical repre- sentation of those parameters. 5 ul injections of a 1 ng/ul 525 standard mix (AccuStandard) with 5 ng/ul of internal stan- dards were run. Notice, in Figure 1, that the initial oven temperature was 90°C. Nor- mally, to take advantage of the solvent effect, an initial oven ‘temperature of 10-20°C below the solvent boiling point is used. The solvent in this case was acetone (BP 56°C). Thus, a typi- cal initial oven temperature would be 45°C. ‘Temperature and Pressure Profiles for the 2051. “Pressure Pulse" Technique INLET PRESSURE SUNLVUGNL N3AO fo 5 » 5 2 % x sec RUN TIME ACQUISITION PARAMETERS. INLET: S0PSIfor 1 5iminutes $8 PS¥nin to 54 PS then constant flow at 30 em/see PURGE VALVE ON at 15 minutes INJECTION PORT 230°C oc: 90°C for2 minutes 35°C /min to 130% | A2Chmin wo 10°C 8°C/min to 320°C; 435 minute hold Ms: sean 45-450 amu, A/D=2 | star acquisition at 4 minutes EM 500 above DFTPP tune | TRANSFER UNE 2a5°0 Figure 1. The GOMS parameters ‘used in the large volume injection experiments. An HP 971A with an HP 5980 Series 1 GC vwas used. (When the Inlet pressure program is ‘shorter than the GC oven, Program the GC will go Into the constant flow ‘mode automatically.) Figure 2, ‘The pressure and temperature profiles for the EPC ‘experiments. Figure 3 shows what a normal, _30 psi initial injection port pres- constant pressure (flow sure followed by constant flow. decreases with oven tempera- _ Figure 4 shows the optimum ture) 51] injection would look conditions for both constant flow like at 45°C. Only 70% of the and constant pressure. Note total sample is transferred, and that electronic pressure pro- the chromatographic peak shape gramming (EPP) decreased the is unacceptable. By raising the run time and inereased the reso- initial oven temperature to lution. This is especially appar- 90°C, the peak shape improves _ent in the late eluting peaks. remarkably, but now only 80% of the sample is transferred. ‘These data show that optimizing Finally, the optimal tempera- _splitless injections can improve ture of 70°C gave a sample GC/MS sensitivity with or with- transfer of 90%. When larger __ out EPC, but EPC with pro- volume injections are necessary, gramming gives the best results. try raising the initial oven tem- These data confirm that larger perature 10-20°C above the volume injections are possible solvent boiling point for better _with optimization. So, at the GC peak shape. end, the proper choices of col- umn, liner and pressure control These constant pressure per- _can greatly improve the amount centages were compared to of sample that is transferred to 100% transfer of sample with a __the mass spectrometer.LARGE VOLUME INJECTIONS WITH CONSTANT PRESSURE. ‘94h 525 rx w/ 5 ng STDs Nps constant esse, 48°C 7% ‘51 ll 525 ix w 5 gh STDs 1 pl constant presnure, SOC oon ‘54 Sag 625 ni w 5 ldSTOs Mp cortan presse, 70°C 0% Tine ind Figure 3. Total ion chromatograms of a 525 standard mix showing the importance of initial oven temperature. Only the first 20 minutes are shown to more easily view the chromatographic peak shape. COMPARISON OF CONSTANT PRESSURE AND PRESSURE PULSE ‘Aoandance 54 Ing 525 mi w SnghlISTDs Msi conta oresure, 70" =| oom 5 Wold 825 mic wi mp STDs 30 ps intl pressue pase, 90% omce on “Tine tint Figure 4. Two total ion chromatograms comparing constant pressure and pressure pulse followed by constant flow. The full chromatogram is shown. Note that the lower chromatogram (constant flow) has a run time of -25 minutes with but the upper chromatogram (constant pressure) does not finish until 27 minutes,HEWLETT PACKARD Hewlett-Packard shall not be liable {for errors contained herein or for incidental or consequential damages in connection with the furnishing, performance or use of this material. Information, descriptions and speci fications in this publication are sub- Ject to change without notice. (23) 5001-54938 Printed in the U.S.A. (9192)(iy HEWLETT PA PackaARD Automated setting of electronic pressure controlled inlets to standby conditions on the G1030A DOS MS Chem3Station Doug McIntyre MS Application Brief ‘Many GC/MS applications can benefit from using Electronic Pressure Control (EPC), a fea- ture of the HP 5890 Series IT Gas Chromatograph. In some applications using a splitless injection, the sample is injected at a high inlet pressure followed by a fast downward ramp to a more typical pressure. This can help control solvent expansion and reduce residence time in the inlet, improving the transfer of unaltered sample onto the col- umn. A consequence of using this technique however, is that between runs the column pres- sure is high, resulting in greater flow of carrier gas than the mass spectrometer is designed to handle on a continual basis. In on column injections, improved sample transfer can sometimes be obtained by programming the column pressure to a reduced pressure prior to and during injection. Again, mass spectrom- eter and column performance would suffer if the system was left this way between runs, particularly at high oven tem- peratures. For more details on the advantages of EPC and pres- sure programming techniques, see other recent HP Application Notes'*, This note describes a procedure that will automati- cally set the column pressure to a standby value between runs and then reset it to the desired initial pressure before the next sample is injected. Other ways of controlling GC parameters between acquisition runs will also be described. Procedure ‘The G1034C version of the DOS MS ChemStation software has two macros that allow the set- ting of the oven temperature and inlet pressures. These macros can be run from Acquisi- tion interactively by typing on the command line or can be called while running a method or sequence. The macros have the following syntax: OVENTEMP newvalue [sync] where “newvalue” is the desired oven temperature in degrees. G1034C GC/MS Software MS 92-10 Seventy is used if no value is specified. “Sync” determines whether the data system will wait for the GC oven to equili- brate to the new value before proceeding. Zero is the default and means do not wait. Any other number means wait for equilibration of the oven ‘temperature. INLETPRESSURE zone,newvalue where “zone” is “A” or “B” (must be in quotes) and specifies the inlet to be controlled and “newvalue” is the desired new pressure. The pressure units used are those of the current method. These macros can be run inter- actively from Acquisition. Bring up this window by selecting Main Panel from the AcquireData menu of Top Level. Normally, the Command Line is not dis- played in this window. To dis- play it, select Cmdline on from the Control-menu box ( the “.” in the upper left corner). An addi- tional line will appear in theDD HEWLETT PACKARD bottom of the window. To change Inlet B to 7 psi, type | inletpressure “B",7 To set the oven temperature to 65 degrees and wait for it to reach that value type: oventemp 65,1 Suppose your method starts with the GC oven at 20 degrees and you inject at 1 psi followed by a quick ramp to 8 psi. At the end of the acquisition run, the oven will be hot and the inlet pressure will be reset to zero. Using the macro “Postrun,” the pressure will be set to 8 psi until the GC oven has cooled back down to 80 degrees. It will remain at 8 psi and 80 degrees until the system prepares for the next run. This will avoid unnecessary use of cryogenic coolant. The macro “Prerun” is used to set the inlet pressure back to 1 psi and the oven tem- perature to 20 degrees. It is not needed when acquiring data from a method or sequence but itis required when multiple samples are run from the Acqui- sition window. Otherwise the initial conditions will stay at the setpoints determined by the Postrun macro. name Prerun inletpressure “BY,1 oventemp 20,1 return name Postrun inletpressure “B”,8 oventemp 80,1 return For these macros to be executed automatically, they must be stored in special files. The “Prerun” macro should be stored in a file named “msacql.mac.” The “Postrun” macro should be stored in “msacq2.mac.” They should be the only macro in each file. The macros can be written using Notepad. Where these macros are stored is important. Normally, they should be stored in the method directory of the current method. So, if you are running a method called “EPC_PEST.M” and your GC/MS is configured as “Instru- ment 1,” store the macros in the directory: | c\HPCHEM\\MeTHODS\ EPC_PESTM Note that all methods formed by editing this method will also set the GC to the same conditions between runs. To disable this feature, use File Manager to delete “msacql.mac” and “msacq2.mac” from the method directory. ‘To make these standby condi- tions apply for all methods, store the macros in the directory “C:\HPCHEM\MSEXE.” If you have multiple instrument con- figurations for your mass spec- ‘trometer and you only wish the macros to apply to one configu- ration, then store them in the instrument directory. For exam- ple, if you have Instrument 1 and Instrument 2 configured for an HP 5989 and only want the macros to apply in the Instru- ment 2 configuration, store “msacql.mac” and “msacq2.mac” in “C:\HPCHEM\2\5989.” For information on other com- mands that you may wish to use in these macros, see the On Line Help under Acquisition Commands. Important! Your method should not have Constant Flow Mode selected if you wish to use these macros between runs. Otherwise, as the oven tempera- ture cools or heats the set pres- sure will change. Instead, use a pressure program to emulate Constant Flow Mode. References 1, “Improving the sensitivity of your GC/MS system with electronic pressure control.” MS Application Brief MS 92-5 HP Pub, No. (23) 5091-5493E. “Applications of Electronic Pressure Control and Pres- sure Programming in Capil- lary Gas Chromatography” Application Note 228-141 HP Pub. No. (43) 5091-2731E. Hewlett-Packard shall not be liable for errors contained herein or for incidental or consequential damages in connection with the furnishing, performance or use of this material. Information, descriptions and speci- fications in this publication are sub- ject to change without notice. (23) 5091-61806 Printed in the U.S.A. (11/92)Addendum -- HP 5972A Sales Training ManualHP 5972A Mass Selective Detector Sales Training Manual Company ConfidentialWAR packano HP 5972A Sales Training Manual Publication No. (23) 5091-6074EUS December 1992 by Tim Borrego with significant contributions from the MS Marketing Staff and the HP 5972 R&D Team.Table of contents — Introduction 1 ‘What's new 2 Pricing and configuration... 15 Positioning . 18 Competition summary 19 Retrofits .. may Marcom promotions 38 Support... . 39 Conclusion... 40 Appendix 41 FAB's at a glance... . . 41 HP 58904 option #201 ship kit lower level parts voces 44 Maximum sensitivity autotune .. R&D features and specifications sheet ‘Team members if HP Internal Use Only Company ConfidentialIntroduction LL During this 10th anniversary year of the benchtop MSD, SID is proud to introduce the next generation benchtop quadrupole mass spectrometer, the HP 5972A. Over this time period the HP 5970 and 5971 have been the world’s best selling mass spectrometers. ‘The reputation of these products has been based on excellence in reliability, performance and price. The new HP 5972A will continue to build on these advantages as it is the only benchtop GC/MS that provides the total performance labs need. ‘The strongest features of the HP 5972A are listed below: 1. High sensitivity EI and CI which meets or exceeds the competition with published proof statements in the specification sheet for EI- full-scan, EI- SIM and Cl. The entire system is optimized to identify trace components in complex matrices, 2. Accurate reproducible quantitation with published proof statements in the specification sheet such as total dynamic range, linear dynamic range, and mass axis stability. 3. True classical EI and CI spectra that stand up to legal challenge and professional examination, 4, Easiest benchtop GC/MS system to learn and use with the intuitive Microsoft Windows and HP-UX interfaces, extensive online help, simple source-cleaning video computer-based training and clear task-oriented user manuals. 5. Superior operating software that offers quick productivity with tools such as application specific Autotunes™, Smart sequencing™ and links to powerful Microsoft Windows and HP-UX software applications. 6. Highest reliability of any GC/MS system on the market, recognized by chemists in independent studies year after year. 7. Most complete automation with unattended analysis using the HP 7673 ALS. 8. Unmatched networking for maximum productivity and true growth paths using HP ChemLAN and Novell. 9. Far superior service and support to keep the system up and running. HP has been the best and we intend to keep it that way. 10. No competitive GC/MS benchtop system can top our price and performance. We will still offer a DOS system bundle for $50K including the HP 5890 Series II GC with EPC and a new enhanced performance GC/MS installation kit (6890A #201). 1 HP Internal Use Only Company ConfidentialNew redesigned detector What’s new ‘Anew detector manufactured by K&M, is comprised of the perma- nently mounted superstructure and electron multiplier horn. We selected the detector based on extensive in-house testing for sensi- tivity, linearity and lifetime. The unique state of the art design optimizes ion optics by “steering the ions” off axis into a broad horn for high ion collection efficiency while reducing sensitivity to back- ground noise. The bottom line is that the detector offers enhanced sensitivity and a greater linear dynamic range. Maintenance is inexpensive and extremely easy since the electron multiplier horn can be snapped out of the permanently mounted superstructure and replaced in seconds. Existing tunes such as DFTPP, BFB, and standard spectra tune are all compatible with the new detector when used on a HP 5972A or HP 5971A. The detector is not cur- rently supported on the HP 5970B or MS Engine. Power supply to the multiplier is computer controlled from 0 to 3,000 volts in 12.5 volt increments. Detector (superstructure and EM horn) 05971-80102 $895.00 US List EM horn replacement 05971-80108 TBD 2 LHP Internal Use Only Company ConfidentialExtended mass range —_ Scanning mode — Scans any mass range between 1.6-700 amu in 0.1 amu steps. The mass range of the HP 5972A has been extended to 700 amu. This increased mass range is of particular interest for certain doping applications such as the analysis of a derivative of the anabolic steroid stanazolol. Another reason for going to 700 amu is to differentiate us from the ion trap which can only scan to 650 amu, We are doing more extensive testing of our quads to accommo- date the extra 50 amu range. Redesigned vacuum manifold and o-ring ‘The vacuum manifold is now machined from billet aluminum and provides considerably less porous surface area. The reduced surface area reduces the time necessary to achieve a clean vacuum with low water and hydrocarbon background. In addition, the redesign accommodates a new o-ring and includes a one piece connection for the ion gauge tube to prevent air leaks and improve reliability. The ‘o-ring replaces the boot seal and is similar in design to the one used on MS Engine. The o-ring is made of Viton and therefore will not off-gas as much as the old boot seal due to lower surface area exposed to vacuum. By minimizing Viton exposure to vacuum, background contamination is also reduced. 3 HP Internal Use Only Company ConfidentialVacuum system ‘The HP 5972A uses highly refined Inland 45 rough pump fluid for reduced hydrocarbon background. A super-refined low vapor pres- sure Santovac 5P Ultra (CysHz,0, MW 354.15) diffusion pump fluid decreases the background over the entire mass range by an order of ‘magnitude compared to the conventionally available Santovac 5. ‘The 2, 3 and 4 ring polyphenyl ether components of Santovac 5P Ultra (MW 170, 262, 354 respectively) not only reduce background in the high mass region of the spectrum but also indirectly reduce the low mass “grass” which results from their fragmentation and decomposition. These oils may also be used in HP 5971 MSD pumps. Diffusion pump oil (Santovae 5P Ultra 18mL) 6040-0809 $108.00 US List Rough pump oil (Inland 45) 6040-0798 $195.00 US List Analyzer vacuum is maintained by a new Edwards E2M2 that replaced the Alcatel E2M1 earlier in the year. The air-cooled diffu- sion pump is backed by a two-stage direct drive mechanical pump (Fisons MD-800 uses an Edwards E2M1). Overall system pumping speed is approximately 60 liters per second for helium. Vacuum system can accommodate a capillary flow rate of 2.0 mL per minute of helium. Pump-down from atmosphere to operating pres- sures requires approximately 10 minutes to get spectra. Venting the system to atmospheric pressure requires approximately 20 minutes, the exact time depends on the temperature of the GC/MS interface. Pump down/vent cycle is accomplished by following a simple proce- dure incorporated in the software. The recommended but optional ion gauge controller monitors pressure in the high vacuum chamber up to 1 x 10 Torr. Typical chamber pressure is 5 x 10“ Torr depending on column flow rate. 4 HP Internal Use Only Company ConfidentialEnhanced HP 5890A option 201 (shipkit for use with Mass Spec) New maximum sensitivity autotune Various new items have been added to option 201 which increase the GC/MS system sensitivity of the HP 5890 GC used with the HP 5972A, 5971A and 5989A mass spectrometers. These items include a new 30 meter “low bleed” column (HP part number 19091S-433), a deactivated splitless liner, moisture and oxygen traps, a Merlin microseal septum, instructions on how to optimize the HP 5890 GC for high performance MS analysis, a column cutter, the appropriate ferrules, nuts and other assorted items. Please refer to the Appendix for a complete list of items. ‘We also recommend that you have the customer order electronic pressure control (EPC) on the HP 5890 GC, as among other things it will allow up to a 5 microliter sample injection to help meet any sensitivity requirements. Note: The HP 5890 GC options (#039, #110, #201, #580) are all bundled together under option #605 which also includes a 17.7% discount over the sum of the individual options. Please refer to the Pricing section of this document for a detailed pricing breakdown. GCMS performance kit (same as HP 5890 #201) 05890-61455 $1,200.00 US List Note: Please refer to the Appendix for a complete lower level parts breakdown. Because of the new analyzer parts, the HP 5972A will require either the HP G1034C MS ChemStation (DOS series) software or the MS ChemSystem (HPUX) software (HP 59944B version B.07, and HP 59944C version C.02). Included in the software is a new maxi- mum sensitivity autotune. This autotune basically accomplishes what many customers do when they manually tune their instru- ment for maximum sensitivity. The tune differs from the original standard spectrum autotune in that it uses wider peak widths and optimizes the repeller and entrance lens in a different manner. ‘The net effect on spectra is an increase in signal at the low- and mid-mass ranges with little change in the high-mass. Other modifi- cations in the software that enhance sensitivity relate to data aquisition and have a net affect of decreasing noise in the spectra, 5 HP Internal Use Only Company ConfidentiatNew SmartCard Hardware manual New look — Note: This autotune can be used on HP 5971A GC/MS systems but be aware that customers will see pronounced differences in their spectrum that they are not used to. Refer to the Appendix of this document for an detailed explanation and an example of the maxi- mum sensitivity autotune. ‘A new second generation on-board computer (HP-IB/MS control ‘SmartCard Il) provides increased data buffer storage for enhanced operation with the DOS and HP-UX multitasking data systems. ‘This feature will provide better multi-tasking to all applications by freeing up the main PC. Note that the Real-Time-Clock will actually be shipping with the first release, but will not be used due to the lack of host software support at this time. — aes ] il Kost comPuTER (us.008 0 UN CHEUSTATION | | wan ever | Ld | siscrmones | __ oo | MASS | ‘SPECTROMETER ‘Sor2A Anew hardware manual will provide the most up-to-date infor- mation to the user. A new task oriented and graphical approach makes procedures easier to follow. Quick start up and preventative maintenance will be stressed along with a systems approach to troubleshooting. Hardware manual 05972-90001 ‘To enhance the overall image of the HP 5972A MSD as a new prod- uct, a new cover has been designed that will include status lights for power on/off, analyzer on/off and calibration valve on/off. Main- tenance will also be facilitated with the new “pop off” top cover. 1, Power: the MSD rear panel power switch is on (green) Details: this light should always be on when the instrument power switch is on. 6 HP Internal Use Only Company Confidential2. Analyzer: the quadrupole mass analyzer is active when the light is on (yellow) Details: this light is activated by a software request for the mass spec analyzer to turn on via the MSON command. Whether the filaments or detector are active at this time depends on the mass spec parameters that have been set in TUNE. This light should be on during a GCMS run (after the solvent delay) and during tuning when profiles, lens ramps and scans are being executed, The light will turn off when an MSOFF command is executed or after the time-out delay. 3. CalValv on (yellow) the PFTBA calibration valve is open when the light is Details: this light is activated by a software request for the mass. spec analyzer to turn on via the MSON command when the CALVALVE parameters in TUNE is set to ON. The light will turn off when an MSOFF command is executed or after the time- out delay. POWER — ANALTZERCALAIVE = = a ~ x oe = 7 HP Internal Use Only Company ConfidentiatNew specifications Full sean sensitivity — electron impact ionization ‘When scanned at approximately 425 amuw/second over the mass range 50-300 amu, the HP 5890 Series I] GC/5972A MSD will pro- duce a signal-to-noise of at least 10:1 RMS (2:1 peak-to-peak) on 10 pg of hexachlorobenzene, injected in the splitless mode when the signal-to-noise is measured using the extracted ion at 283.8 #/--0.3 amu, This specification is valid only when using a low-bleed column such as HP product number 19091S-433 (shipped with the instrument) or equivalent. i Ton 283 60 [283 50 to 284 10): HCB10PG.0 (2500 | | 2000 | | | 1500 HP 59724 “SD | s000 4 500 | hapa acpiny Mea pine WMeeaadaraprdab habe Ansel ar bo 7.50 8.00 8.50 9.00 9.50 Wverage of 6.539 to 8.579 min ACHIOeG.O TF, =, ¥ 40 pg hexachlorobenzene, scan node 10 pg hexachlorobenzene, scan node He 5972A MSD 8 HP Internal Use Only Company ConfidentialAnother benchmark test of sensitivity is found in the analysis of dioxins in the environment. It is desirable to be able to routinely analyze dioxins to the low picogram level on column. Below is shown ‘a signal to noise ratio of approximately 6:1 rms for 100 fg of 2,3,7,8 tetrachlorodioxin. om 31989 ama rom A2_10t52 10045 1CO0; Fun at 1096 AM POT on Thu Oetoe, 1002 : Fo hd, I \ Vwi ab apo ad ivan 3 on 32120 ama rom A2_ 10024 9 HP Internal Use Only Company ConfidentialScan sensitivity — chemical ionization When scanned at approximately 405 amu/sec over the mass range 80-230 amu, the HP 5972A MSD will produce a signal-to-noise of at least 10:1 RMS (2:1 peak-to-peak) on 20 pg of benzophenone, injected in the splitless mode when the signal-to-noise is measured using the extracted ion at m/z 183.1 + 0.3, using methane as the reagent gas. The spectrum not only includes the molecular adduct ion (M + HI at m/z = 183, but adduct ions (M + CyH.J* at m/z = 211 and [M + CsH,}' at m/z = 228. Using a variety of reagent gases, CI provides molecular weight in- formation plus increased sensitivity and selectivity for many com- pounds. With methane reagent gas, true, classical, positive-ion CI spectra are produced with strong adduct ions to confirm molecular weight determination (see figure on next page). Adduct ion forma- tion is generally not obtained when using ion trap mass spectrom- eters, thus making molecular weight determinations less definitive, particularly in complex mixture analysis. 10 HP Internal Use Only Company Confidential—. ibungance = Ton 183.10 (182.80 to 183.40): BENZO.D 300 3000 ou 20 pg benzophenone, methane CI made 2000 ¥® 59724 Hs 1500 | 4000 500 | | | | Ti/cibenz \ 0 oo "5.20" "5.40 5.60 ‘Average of 6 bo 6.00 6.20 "5.40 6.50 6. S to 6.185 min BENZO.0 Tane--2 5. SengebbS ano) 20 pg benzophenone, methane CI mode ed HP 5972A MSO | 1000 800 600 108 400 2004 119 98 Fn ee ug at“ vea174 Theis fla dll f: i 809) "100 440 120 130 140390160 1/0 180 igo 200 “210 220, tl Note: The PCI specification of the HP 5971A was performed using methyl stearate not HCB; 10 pg MeSt, 10:1 s/n RMS. Note: Chemical ionization (G1072B) will not be available on the HP 5972A at introduction but will follow in the upcoming months. ul HP Internal Use Only Company ConfidentialSelected Ion Monitoring (SIM) sensitivity — electron impact ionization When monitoring m/z 283.8 +/- 0.3 using low mass resolution, 500 msec dwell time, the HP 5890 Series II GC/5972A MSD will produce a signal-to-noise of at least 10:1 RMS (2:1 peak-to-peak) on 200 fg of hexachlorobenzene when injected in the splitless mode. ‘This specification is valid only when using a low-bleed column such as HP product number 19091S-433 (shipped with the instrament) or equivalent. No other benchtop vendor publishes a SIM spec. Pr TIE ACBOS-0 250 | | 200 fg nexachlorobenzene, SIN mode He 59724 MSD en | . Cl ane-8.10 6.15 620 6.05 6.50 68 6.40 8H 65) 655 660 Bb B10 875 2 HP Internal Use Only Company ConfidentialThe reproducibility of the HP 5972A is shown by the very stable qualifier ion ratios for 125 consecutive injections of a THC metabo- lite over 31 hours. ‘The Mass Axis Stability of the HP 5972A is +/-.15 amu over 12 hours of normal operation. Note that the mass axis stability, and thus the ion ratio stability, depends on maintaining a constant operating temperature. Data of this quality are possible only when the laboratory temperature is rigorously controlled. THC ion ratios, SIM mode. 125 injections over 31 hours £ £ 5 5 Pom meee eee meee eee. — 80% 100.00 Ratio 357/372 50.00 00 Wednesday 12:00AM 6:00AM 12:00PM 6:00PM 12:00AM 6:00AM 12:00PM 6:00PM 12:00AM Time of day 13 HP Internal Use Only Company ConfidentiatThe HP 5972 Dynamic Range calibration is linear over 4 orders of magnitude. Total ADC Dynamic Range is 10°. The linearity of the HP 5972A is shown by the very stable area response factors of Anthracene over 4 orders of magnitude. yooo000000 o~ Anthracene calibration, 10-100000 pg ‘0000000 10000000 vo00000 Area response 100000 10000 10 100 1000 10000 ioo000 Amount injected (pg) Increased scan speed Instrument provides for maximum scan rates to 1800 amu/sec ‘on both the DOS ChemStation and HP-UX ChemSystem with 0.1 amu mass resolution. The competition sets scan rates consider- ably higher (MD-800 6000 amu/sec, ion traps 5600 amu/sec) but this is the rate the analyzer scans at, not the usable scan speed. Typical analyses require one scan/second. For a HP 5972A, this would be 700 amu/second, well within the capability of the instrument. 4 HP Internal Use Only Company ConfidentialPricing and configuration Part number US list FBP MSD Mainframe Mass Selective Detector 5972A $32,000 $80,780 Note: The ion gauge controller is no longer available as option #400, instead order 598228. Power cord options ‘Must specify power option from list below: S972A #Axx NIC Nic United Kingdom ABU Australia/New Zealand/China ABG European ABB United States ABA Canada ABL Switzerland AcD Denmark ACE South Africa/India ACQ Japan ACF MSD options and accessories Ton Gauge Controller 598228 1,500 1,485 Note: Chemical ionization (G1072B) will not be available on the HP 5972A at introduction but will follow in the upcoming months. MSD-IRD options and accessories MSD-IRD Interface 5972A #060 5,900 5,100 MSD-IRD Interface (Field Installed) 597658 5,900 5,100 IRD-CI Accessory Kit G1072A #001 NIC NIC Approximately 50% of our IRD units are sold in conjunction with an interface to accommodate GC/IR/MS analysis. The ability to provide this complementary information conveniently from a single injection is a major advantage for HP in the GC organic qualitative analysis segment of our market. Screening of complex total unknowns and isomer determination by the combination of MS and IR are espe- cially useful to this market. 15 HP Internal Use Only Company ConfidentialBundles Cost savings information for HP 5890 option #605: Option Description Price #039 EPC board $995 #110 Capillary Inlet for Split/Splitless w/EPC $2,465 #201 For use with the Mass Spec $1,200 #580 HPIB for DOS, HP-UX $920 Subtotal #605 Discount % #605 Discount #605 Price Bundles are a very cost effective solution for both our customers and HP, they offer many advantages: ‘+ FE can focus on selling APG instrument solutions, not Vectras * Qualify for GSA contract pricing + Easy to quote, order, install, and support; cleaner orders + Vectra is shipped with every system bundle + Bundle ships totally integrated (all SW loaded) from the factory ‘+ Customer delivery time improvements + Customer satisfaction 16 HP Internal Use Only Company ConfidentialMSD DOS ChemStation bundles Part Description number = USLCP RP Educational G1019B ‘$39,000 $35,320 Includes HP 5972A MSD, Vectra 386 5/20, SuperVGA, color VGA monitor, 4MB RAM, 120MB disk, 3.5” floppy drive, operating software, DOS, Excel, Windows, DeskJet. 500 printer. Specify power option (#Axx) Entry 10208 $44,000 $40,280 Includes HP 59724 MSD, Vectra 486/33U, UltraVGA+, color VGA monitor, 8MB RAM, 240MB disk, 3.5" floppy drive, operating soft- ware, DOS, Excel, Windows, LaserJet IIIP printer. Specify power option (#Axx). Standard 10218 $48,000 $44,250 Includes HP 5972A MSD, Vectra 486/66U, UltraVGA, color VGA monitor, MB RAM, 430MB disk, 3.5" floppy drive, operating software, DOS, Excel, Windows, LaserJet III printer. Installation, ARCS (US/Can). Specify power option (#Axx) All DOS bundles include the HP 59724, Mustang III operating soft- ware, Microsoft DOS 5.0, Windows 3.1, Excel 4.0, installation and ARCS. Bundles differ in respect to the Vectra computer and printer. Customers can then choose the best ChemStation based on their budget and productivity requirements. DOS ChemStation bundles are based on the popular PC platform with an easy to use Microsoft ‘Windows interface. Note: MSD HP-UX ChemSystem Bundles will appear at a later date. 17 HP Internal Use Only Company ConfidentialPositioning ‘The HP 5972A is an evolutionary product based on the HP 5971A. The HP 5971A has been the second most successful benchtop mass spectrometer in history (behind the HP 5970A/B) and competes in the low cost segment of the market. The HP 5971A was initially introduced in 1988 and has undergone a number of hardware ‘enhancements including the following: + Larger more reliable E2M2 rough pump + Extended dynamic range board increased dynamic range 8 fold + G1072A Chemical Ionization * Increased Ion Focus voltage range + Lowered minimum Entrance Lens value + Added temperature compensation to quad driver cireuit Future improvements of the HP 5972A series will continue to focus on sensitivity, mass range, faster scan speed, and higher column flow rates. Other improvements may include NCI, rapid EV/CI switchover and separately heated ion source. MS Engine (HP 5989A) is targeted toward the mass spectrometrist and advanced chromatographer who runs samples in research, central service and method development labs. These labs are look- ing for a combination of performance (primarily sensitivity), and flexibility with various inlet techniques (GC, LC, Electrospray M! probe). 18 LHP Internal Use Only Company ConfidentiatIntroduction Competition Thermo Instruments Finnigan) Competition summary The competitive arena for benchtop MS systems has become very fierce in the past few years. Direct sales for the benchtop GC/MS market are expected to grow at a compound annual growth rate of 5% for the next decade. MS vendors who have typically focused on free-standing research grade systems are introducing benchtop GC/MS systems with a marketing focus towards the environmental and drug market places. Many are writing application specific soft- ware for markets such as pesticides, drugs, and air toxics. ITS 40 — Introduced 1989 Historically, Finnigan has been the strongest competition for HP. They have the broadest product offering of all the MS instrament manufacturers. Their recent acquisition by Thermo Electron has slowed business and they have been forced into layoffs and major ‘cutbacks. Management is being pressured to maintain a 20% oper- ating profit. Finnigan is downsizing and has lost many good employ- ees in sales and service. Their service organization has never been as good as HP's especially outside the U.S. and these factors will not help. Finnigan at Pitteon 92 introduced two packaged solutions aimed at the pesticide market (Tracker) and environmental market (Magnum). Both are structured around the ITS 40 with the only differences being the PC, software libraries and standard CI (supposedly improved) on Magnum. Finnigan is obviously using all the creative marketing ideas that it can to win business, while trying not to revisit the failing Witness drug testing package. Strengths * Scan sensitivity * Scan speed ‘+ Target compound analysis software + Turbo molecular pump + Fast software © Witness drug software * El to Cl switching time 19 HP Internal Use Only Company ConfidentialWeaknesses + Non-classical EI spectra * Self CI effect ‘+ No Single Ion Monitoring (SIM) + Non-classical CI spectra (No adduct ions to confirm MW) * Problems analyzing dirty samples (matrix effect) lovers sensitivity) + Problems analyzing target compounds with co-eluting internal standards * Difficult to customize software * Software is not Windows based * System is not a single vendor solution + No DFTPP or BFB target tunes Hardware issues Finnigan may try to push the fact that the quartz quadrupole can- not be cleaned. Most Finnigan reps do not use this anymore because it started to backfire as the customer started to think about cleaning dirty traps. The reason why we do not clean our quads is that typi- cally they don't get dirty. Our specially designed ion source with ‘Turner-Kruger lens (pre-filter) design takes the brunt of the impuri- ties. Reference your installed base customers to verify that quad cleaning is not an issue. CT on the ITS 40 (“advanced CT”) is not the same as for the Varian Saturn IL. The Saturn II uses the old version of CI, whereas the ITS 40 uses the new version. This difference was part of the dispute between Varian and Finnigan. The old version of CI worked by trapping all ions in the trap, including methane ions to react with the sample itself, storing these ions and allowing the methane ions to react with the sample molecules to form CI sample ions then ejecting the ions to give a CI spectrum. The spectrum that resulted was a “mixed mode” spectrum, containing both El and CI features from the sample because the sample ions were stored in the trap during the ionization of the methane to produce the methane reagent gas ions. Advanced CI changes this process by using a different scan fune- tion for the formation of the reagent gas ions. All ions are formed when the electrons are entering the trap, but the scan function then ejects all ions except the reagent ion for methane (mass 17). Then the voltage is changed to trap all ions, and the reaction between methane reagent ions and the sample molecules occurs and the products stored. The resulting spectrum is thus devoid of ET character. 20 HP Internal Use Only Company Confidential‘There are still no adduct ions formed in this process because masses 29 and 41 are not formed at the pressures used in ion trap CI. Finnigan will fight our statements of “non-classical CI” by saying something similar to the following: “Masses 29 and 41 are really artifacts of the fact that one has to use high pressure in the old design CI sources. The Finnigan technique of advanced CI avoids formation of these artifact “adduct ion” peaks, is “pure CI,” and is actually less confusing and a superior way to do CI. The older sources needed higher pressures of methane to perform efficiently, but due to the breakthroughs of the high-efficiency ion trap technol- ogy, one may perform very sensitive CI without the high pressure and without forming the artifacts present in the previous MS.” The Finnigan rep may push that the MSD cannot switch between EI and Cl very easily. Actually, a customer can change from EI to Cl in an HP 5972A in 30 minutes, however it will take several hours to purge and equilibrate the system for proper CI operation. We sug- gest that this be done in the evening and allowed to equilibrate overnight. The procedure is not complicated. It is unlikely that the customer will need to change back and forth during the day anyway 30 whether he has a Finnigan quick-change instrument or an HP 5972A the best technique is to run all samples of one type (ED first and then convert to finish the other (CI) samples. The major concern for the customer should be positive identification of the sample. The non-classical ITD spectra can lead to wrong molecular weight interpretation, because in CI molecular ions can be either M+1 or M-1. Classical CI, as you get with the HP 5972A, the M+29 and M+41 ions (for methane CI) will help iden- tify the proper molecular ion. At this time there are no CI libraries offered from any vendor. HP also offers a greater number of reagent gases (Finnigan only lists methane and isobutane). Such choices are sometimes critical to the analysis to obtain the best spectra and confirmation. OT now offers the optional OI Purge and Trap system software working under Windows 3.1 simultaneously with the G1034C soft- ware for environmental analysis. Push the fact that very few labs have multiple ion traps while there are many labs with multiple MSDs. Software issues ITS 40 does not have an industry-standard user interface while our Microsoft Windows based HP G1034C DOS MS software is the third generation software based on industry-standard Microsoft Windows 3.1. ITS 40 doesn’t have easy networking versus our ChemLAN. 21 HP Internal Use Only Company ConfidentiatVarian Finnigan has recently been falsely claiming that Witness has been certified by NIDA (National Institute on Drug Abuse). The fact is that NIDA does not certify instruments, they only certify laboratories. Point out the fact that 88 out of 90 labs that have this certification own HP mass spectrometers exclusively. The only lab which uses the ion trap spends a considerable amount of money on expensive special standards because of the trap’s problems with co-eluting deuterated internal standards, the method of quantita- tion normally used by drug testing labs. Application issues ITS 40 has problems with correct isotope abundances. Have your customer compare to published referenced spectra from com- pounds such as polyhalogenated materials, e-g., PCBs to what is demo’d or shown by Finnigan. The high ITS 40 sensitivity is only really useful in a clean matrix such as drinking water analysis or air toxics. In a complex matrix such as soil, sludge, physiological fluids and food, the HP 5972A is much more successful ITS 40 spectra are non-classical (esters, cocaine, heroin). ‘Although they claim to have solved this problem, the effect has been. downplayed and disguised, not fixed. Have your customer compare ITS 40 spectra to published reference spectra. ITS 40 “self-CI” has been recognized by many laboratories. CI spectra do not contain any adduct ions and are therefore not classical using methane reagent gas. The CI spectra from HP 5972A contains adduct ions which confirm the molecular weight. HP also offers a greater number of reagent gases. Such choices are sometimes critical to the analysis to obtain the best specta and confirmation, When competing against Tracker be sure to mention that HP offers the HP Pesticide Library which includes hard copy extraction proce- dures and methods for pesticides done on an HP 5970B instrument. Saturn II GC/MS Ultra Trace Analyzer — Introduced 1990 Saturn Air — Introduced 1992 ‘The Saturn II is basically a Finnigan ITS 40 (except CI and ALS) but it is manufactured completely by Varian. It is a descendant of the Saturn GC/MS system which was introduced in 1990. The first Saturn system, comprising a Varian 3400 GC and a Finnigan ITS 40 ion trap, was built for Varian by Finnigan MAT through an agreement in 1989. In 1990 Varian purchased the ion trap technol- ogy and began building the Saturn II system themselves. The two companies during 1990 were involved in litigation over delivery and withholding of technology and have since broken all ties with each 22. HP Internal Use Only Company Confidentialother. According to Varian sources they have modified the ion trap and have eliminated some unnecessary hardware features to lower the price. The original Saturn system sold for $87K, the Saturn II costs $76K. At Pittcon '92, Varian like Finnigan also showed a complete solution package called Saturn Air aimed at the air toxic market with a price of $85K. Built around the Saturn I, the system has an air sampler/ concentrator built into their gas chromatograph. They claim it offers the most sensitive GC/MS analyzer for Method TO-14 and thus requires a very small sample size. At ASMS '92, Varian presented a paper by S.E. Buttrill showing a prototype unit performing SIM analysis at a 25 fentogram level for HCB. Strengths * Scan sensitivity * Scan speed ‘+ ‘Target compound analysis software * Turbo molecular pump © Fast software ‘+ El to Cl switching time - important to drug labs, * SPI injector (25 ul injections) ‘+ Supports Tekmar purge and trap Weaknesses * Non-classieal EI spectra * Non-classical CI spectra (self CI effect) * No Single Ion Monitoring (SIM) * Problems analyzing dirty samples (matrix effect) + Problems analyzing target compounds with co-eluting internal standards * Difficult to customize software * Software is not Windows based * System is not a single vendor solution + No DFTPP or BFB target tunes Hardware issues Saturn II has problems with correct isotope abundances. Have your customer compare results to published referenced spectra. ‘The Varian rep may tell the customer that the MSD cannot switch between El and Cl very easily. Actually, a customer can change from EI to CI in a HP 5972A in 30 minutes, however it will take 23 LHP Internal Use Only Company Confidentiatseveral hours to purge and equilibrate the system for proper CI ‘operation. We suggest that this be done in the evening and allowed to equilibrate overnight. The procedure is not complicated. It is, unlikely that the customer will need to change back and forth during the day anyway so whether he has a Varian quick-change instrument or an HP 6972 the best technique is to run all samples of one type (EI) first and then convert to finish the other (CD. samples. The major concern for the customer should be positive identification of the sample. The non-classical Saturn spectra can lead to wrong molecular weight interpretation, because in CI molecular ions can be either M+ or M-1. Classical CI, as you get with the HP 5972A, the M+29 and M+41 ions (for methane CI) will help identify the proper molecular ion. At this time there are no CI libraries offered from any vendor. OT now offers the optional OI Purge and Trap system software working under Windows 3.1 simultaneously with the G1034C soft- ware for environmental analysis, Push the fact that very few labs have multiple ion traps while there are many labs with multiple MSDs. Software issues Saturn II does not have an industry-standard user interface while our Windows based Mustang III is the third generation soft- ware based on industry-standard Windows 3.1. Saturn II has no easy networking versus our ChemLAN. Application issues The high Saturn II sensitivity is only really useful in a clean matrix such as drinking water analysis or air toxics. In a complex matrix such as soil, sludge, physiological fluids and food, the HP 5972A is much more successful. Saturn II spectra are non-classical (esters, cocaine, heroin). Although they also claim to have solved it, the effect has been downplayed and disguised, not fixed. Have you customer compare Saturn II spectra to published reference spectra, Saturn II “self-CI” has been recognized by many laboratories. CI spectra do not contain any adduct ions and are therefore not classical using methane reagent gas. Varian only lists methane and isobutane as reagent gases. The CI spectra from HP 5972A contains adduct ions which confirm the molecular weight. HP also offers a greater number of reagent gases with which to use (Varian only lists methane and isobutane). Such choices are sometimes critical to the analysis to obtain the best specta and confirmation. 24 HP Internal Use Only Company ConfidentialPerkin-Elmer Q-Mass 910 — Introduced 1991 With their instrument the Q-Mass 910, PE is definitely attacking our base business, the MSD. This instrument is priced just under the HP 5972A starting at $43K U. S. PE’s marketing strategy is directed toward the environmental market promoting their “high uptime, ease of maintenance, and simplicity of operation.” Currently they are guaranteeing customers just about anything and discount- ing heavily to get the @-Mass 910 into laboratories. At Pittcon '92 no notable changes were observed and they are only a threat to the HP 5972A in those situations where customers are either not very familiar with MS in general, are very price sensitive or are proprietary PE customers. The system may still be OEM’ed from Leybold, although rumor has it that they will be transferring manufacturing to PE. The system may be more sensitive than the published specs, which are very conservative. Strengths * Fast pumpdown <10 min * Chemical structures in NIST library Disposable ion souree, easily removable DFTPP + BFB Tuning Single vendor solution Weaknesses + Sensitivity * No Chemical Ionization (CI) * To change filament you must change ion souree; it has only 1 filament * Software — “Lotus like” poor menu driven software Hardware issues Use the advantage of our optional OI Purge and Trap in environ- mental analysis. This works in the Microsoft Windows environment of HP ChemStation (DOS Series). PE will push the turbo molecular pump to customers because of speed and capacity. The oil diffusion pump we use has the same 60 Lis capacity as their turbo pump. Oil diffusion pumps are almost maintenance free while the turbo must be oiled on a regular basis. Push our better pump reliability and the fact that turbos are very expensive ($5K) and go down about once per year on average greatly adding to their cost-of-ownership (refer to the cost of ownership comparison in the Appendix). 25 HP Internal Use Only Company ConfidentialFisons Instruments (VG) ‘The Q-Mass ion source sits directly above the turbo without a screen or protector. It is very easy to drop parts into the pump. This could become a safety issue. PE will push their easily cleaned and disposable ion source. Shift the conversation to the real issue which is easy maintenance. Dis- posable indicates that the price is low enough to offset the cost of replacement versus cleaning. We don't believe their $300 ion source meets this criteria. A very comprehensive and easy to understand source cleaning video ships with every HP system. HP's Clis a lock-out spec along with EnviroQuant target com- pound software (HP 1032C). Software issues ‘The PE Q-Mass data system is single-tasking, the HP ChemStation is multi-tasking. Force PE to demonstrate the system versus the HP 5972A; their poor software will force the decision. PE Q-Mass does not have the custom report capability that HP's ChemStation offers. Q-Mass does not include a spreadsheet (Excel) similar to the HP MS ChemStation as a standard part of their software. Excel offers the HP customer additional productivity and flexibility in producing custom reports and QA/QC reports. ‘MD-800 — Introduced 1992 ‘VGiFison's MS product line has changed over the years. VG has, always been well known for their research grade mass spectrom- eters and they have competed very well in that market. However, they have been slow coming out with a lower priced benchtop system directly aimed at competing against HP's MS systems. Fisons recently introduced the new MD 800 which will compete directly with the HP 5972A. The system carries the name of Fisons not VG or Carlo Erba which are the two divisions providing the MS. and GC respectively. The MD 800 price starts at $49,900 in the U.S. and the brochure highlights ultrasensitivity (directed at HP), classi- cal spectra (directed at the ion trap), precise quantitation (directed at the ion trap), and productivity. 26 HP Internal Use Only Company ConfidentialStrengths ‘+ Excellent EI Sensitivity-due to low background from photomulti- plier tube (dynolite)and quad pre-filters (10 pg HCB s/n 10:1 peak-peak) * 800 amu mass range + Accepts 4 external signals + Fast sean speed * Library seach results with chemical structures + ECOPAC - environmental CLP “like” forms software + Has CLP forms including disc deliverables * Easy to access to ion source * Offset CI weakness by offering variable ionization energy feature * Very flexible price list Weaknesses * Fisions (Carlo Erba) 8030 GC - 5890 is far superior + No MS Windows or MS Excel * Poor service and support in most countries * Data base software for target compound analysis called “FIND.” + No chemical ionization (CI) ‘+ “Lotus like” poor menu driven software which is not user friendly and is not based on Microsoft Windows. + Turbo pump reliability problems ‘+ Limited linear dynamic range ‘+ Customer education classes are poor, they are only held in Boston * Environmental CLP forms software does not work properly * Autotune does not work well and does not perform mass calibration Hardware issues ‘The MD800 has a different source from the Trio 1000, but the rest of the system is similar or identical (prefilter, quads, Dynolite detector, data system). Since the instrument uses the same quads as the Trio 2000, VG will boast that they offer a research quad in a benchtop. HP's Clis a lock-out specification for the MSD. Explain the advantages of having true classical CI for molecular weight informa- tion, Variable ionization energy (“poor man’s CI”) on the MD-800 will not give adduct ions (because it is not CI) which is important for confirmation. Moreover, one generally has poorer sensitivity when operating at low ionization energy. 27 HP Internal Use Only Company ConfidentiatFisons service, support and training is far below standard. We have also heard reports that service will be a major issue, pos- sibly requiring customers to send the instrument back to the factory for repair. Ask the customer if they have been told where Fisons MS service will come from and then tell him about the #1 leader in the industry. Customer education classes are very poor and are only available in Boston. Fisons will push the turbo molecular pump to customers because of speed and capacity. The oil diffusion pump we use has the same 60 L’s capacity as their turbo pump. Oil diffusion pumps are almost maintenance free. Push our better pump reliability and the fact that turbos are very expensive ($5K) and go down about once per year on average greatly adding to their cost-of-ownership. Fast vent and pump-down will be stressed during a demo. You should remind the customer that although this may seem impressive, temperature equilibrium and the quality of spectra are related. The spectra that is acquired within minutes of a short pumpdown may not be meaningful. Fast delivery probably isn’t a major problem right now as sales are slow. Ask the customer to get a list of installed base customers from the Fisons rep. This should show a distinct lack of presence in high throughput laboratories. Fisons can control their purge and trap by their MS data system. HP can control the OI P&T through MS Windows on the DOS, ChemStation. ‘The dynolite detector is supposedly guaranteed for 10 years but it ‘may have problems with a narrow linear dynamic range. It is extremely expensive to replace ($3-6K). ‘There is a DIP option for the MD800. VG does not have it on the product configuration yet but the device exists and has been tested and mentioned to customers. The DIP port goes in from the front of the instrument and requires that a different plate is mounted. The highly-touted “transputer” is just a “low cost” third-party plug-in board in the PC. It contains a RISC floating-point processor to speed the number crunching and is used primarily for library searches, the HyperSearch feature. The cost is approximately $1,500-$2,000. VG has not done anything special to make this transputer. It is used more as a marketing feature and is intended to impress or confuse the customer into thinking VG has a vastly superior product. 28 HP Internal Use Only Company ConfidentialIn the US, the MD 800 is only quoted with the Carlo Erba GC which is very hard to use. Problems with the GC include: 1, Heated zones don't cool down unless you turn off the instrument, if you tighten anything cold you will get seizing of the parts. 2. Ifyou close the vent valve to save on helium it leaks. 3. Fisions glass injection port liners cost $100 each! If the customer is running 524/525 they will need to replace it daily. The cost of inserts for the HP 5890A are $8 each. 4, Oven cools down much slower than the HP 5890 Series II, it takes around 1/2 hr to come down to 35°C without eryocooling. Software issues ‘The best way to attack the MD800 is via the LabBase data sys- tem, It does not demo well, does not have the multitude of good features and flexibility as the DOS ChemStation. ‘The NIST library is standard with the Fisions MD800, Wiley is optional. HP offers many specific libraries such as the latest NIST, Wiley, Stan, and Drug. All our libraries are constantly being updated and improved by HP. Force Fisons or Carlo Erba to demonstrate the system. Since it is new, they will have difficulty having enough systems to show customers. A common occurance during demos is lock-up of the operating software which may be disguised as a planned system back-up. ‘VG has an autotune, but due to the fact that the source is new, the autotune may not work very well. There is no equivalent of a DFTPP target tune or BFB target tune, this has to be done manually. Moreover, the CLP forms do not work properly. Other software weaknesses include the inability to access non-MS software during acquisition, incomplete target compound software and no manual integration. 29 HP Internal Use Only Company Confdentia!Shimadzu (Kratos) Unicam QP-5000 — Introduced 1992 Shimadzu Analytical (which owns Kratos) is a Japanese firm pro- viding a broad range of analytical instrumentation to the interna tional market. Shimadzu’s greatest strength is in the local Japanese market but they have made inroads into the U.S. and European chromatography markets. Currently their GC/MS systems are not sold in the U.S. Shimadzu manufactures the benchtop GC/MS system called the QP 5000 which is a quadrupole with an integrated data system. ‘The software is non localized in Japanese. AutoMass (previously sold by Delsi-Nermag) Delsi-Nermag went into voluntary liquidation in early 1992 (equiva- lent to Chapter 11 in the USA) and was sold to Unicam just prior to Pittcon 92. According to the chief financial officer of Delsi-Nermag, “the company had not been doing very well and the economic crisis of 1991 further worsened the situation. There's still a good mainte- nance and support business but in manufacturing we cannot com- pete against companies like HP.” ‘At Pittcon 92, Unicam displayed the PC-based benchtop with a Unicam GC on the front end. They claim to offer the highest sensi- tivity of any quadrupole GC/MS, but no information is available on the spec's. 30 HP Internal Use Only Company ConfidentiatBENCHTOP GC/MS SYSTEM PRODUCT PRICING t ims40 | SATURN II HPUXIMSD | (Magnum) {Saturn Air} | wean | wt {Leth | Jomsaw wx [ooh _fwe | f_femssoo} | ars ff aah ia vce “Hh tined) ay "eet “eh 31 AP Internal Use Only Company ConfidentialHP 5972A MSD Fisons MD800 Finnigan ITS 40 Magnum, Tracker, Waness Mass Range 1.6-700 amu 2-800 amu 10-850 amu Sensitivity | El-Hexachlorobenzene | s/n 10:1 ms 10pg | sin 10:1 p-p 10pg sin 10:1 p-p 10pg El-MethyiStearate Not spec’d anymore Not spec'd Not spec’d Cl-Benzophenone s/n 10:1 rms 209g Cl not available yet s/n 10: p-p 50pg EI SIM-HCB s/n 11 rms 200g Not spec’d—called SIM not available Sel. fon Recording Maximum Scan Speed | 1800 amu/sec 6000 amu/sec 5600 sec Resolution Unit resolution throughout | Fully adjustable over the | Better than unit resolution the mass range entire mass range up to | over the entire mass 2000 at m/z 800 range Pumping Diffusion Pump Turbo Pump Turbo Pump 60sec, ultra pure oil 60 Usee, no oil 50sec, no oil Mass Stability 49.15 amu in 12 hrs 20.10 amu in 12 hrs no information Tuning ‘Automatic or manual ‘Automatic or manual ‘Automatic Tuning Data system controlled | Data system controlled (Autotune very poor) lon Source Electron Impact | Stendard (2 filaments) Standard (1 filament) Standard (2 filaments) Chemical Ionization Optional (1 filament) Not available Standard (1 filament) Tem. Heating Through GC interface Independently Independently Other Variable ionization energy 6c HP 5890 Series Il Fisons 8030(Car.Erba) | Varian 3400 Injection ports Spliy/Spitiess, On-col. SplivSplitless, On-col Spli/Splitless, SPI Purge packed | Purge packed, PTV" On-Col,, Purge packed Elec. Press. Contrl, Available | Not available Not available Other Back pres. regulated ‘Max. vol. $00 mL Back pres. regulated *PTV = programmable temperature variable Als Optional 7673 Optional A200S Optional Az00S Maximum samples 350 (linking possible) 200 200 25y/32u support Yes Yes Yes GCIMS Interface Capillary Direct Capillary Direct Capillary Direct Ancillary Detectors into | Yes, thru HP-UX 4 maximum external | None MS Data System detectors interfaced to | the software Mass Fitter Quadrupole Quadrupole lon Trap Material | Mono. Hyper. Quartz Moly Round Rods Pre-Fitter | Entrance Lens 4 RF only “mini quads” Post-Fitter | Other | ‘Axial Modulation continued on page 34 32 HP Internet Use Only Company ConfidentialVarian Saturn I Perkin-Elmer ‘Shimadzu OP 5000 Saturn Air Q-Mass 910 10-650 amu 1-650 amu 10-700 amu sin 1021 p-p 10pg s/n 10:1 p-p 10ng Not spec'd Not spec’d s/n >30:1 @ 100 pg myz~= 298} s/n 10:1 p-p 50g Not available ‘SIM not available Not spec’d 5600 y/sec 2000 amu/sec 6000 amu/sec Better than unit resolution over the entire mass range Turbo Pump 50 Usec, no oil No information ‘Automatic Tuning Standard 2 filaments Optional filament Independently Varian 3400 Spliv/Splitiess, SPI On-Col., Purge packed Not available Back pres. regulated Saturn Air has variable ‘temp. abs. trap ion trap Optional Varian 8100 200 Yes Capillary Direct None lon Trap ‘Axial Modulation Unit mass resolution over the entire mass range Turbo Pump 50 Usec, no oil No information Automatic or manual Data system controlled Optitune for DFTPP and 8FB Standard 1 filament Not available Independently Disposable ion source Autosystem or 8000 SplivSplitiess Purge Packed Not available No On-column Built in No information Yes Capillary Direct None Quadrupole ‘SS or Moly None None Unit mass resolution Turbo Pump 50 Usec No information Automatic Tuning Standard 2 filaments Not available Independently GC-17A Split Spiitess, On-col Purge packed Not available Anc-14 No information No information Capillary Direct ‘No information Quadrupole } Moly Round Rods No information No information 33 LP Internal Use Only Company ConfidentialFeatures HP 5972A MSD Fisons MDB00 Finnigan ITS 40 Other names Magnum, Tracker, Witness Detector Continuous dynode Dynolite photomultiplier | Continuous dynote Total dynamic range ‘Sample Probes Computer CPU RAM Memory Operating System Disk Drive Printers Terminals Disk Storage Libraries EPA CLP Target ‘compound software System Pricing Installation Warranty Cost of Ownership/year °% of Hardware $ Software updates Service call price Training/Consukting Phone Support electron multiplier 65x10 None 386 or 486 HP Vectra 20, 33, 50 MHz avail 4,8MB Windows/DOS XWindows/HPUX Mutt-tasking 120-440 MB DeskJet, LaserJet Il ‘VGA Color 120 MB internal tape NIST, Wiley, Drug, Pesticide EnviroQuent—DOS Target?2—HPUX $$49.9K (DOS}-S81K (HPUX) Included 90 days santé 8% s24o/year ‘s165/hr + zone Instruction includes 5-day operator course {$1,750 (AEC), on-site ‘consulting at $1,600/day Technical phone assis- tance for warranty and wiadditional response line ‘contract ($87/mo), 40x10" None 386 or 486 Intel PC 16 MB Lab-Base 2, Lotus-like Transputer, RISC technol- ogy, crashes easily 80-1300 MB. Okidate Dot Matrix Laser optional VGA Color Optionat NIST, Wiley, Pfleger, Forensics CLP drug and environ- mental forms, very problematic | $53K and up Included 90 days $5,500 10% Included with hardware contract S165/hr very poor, most use 3d party 3-day operator course included in price. 2-day CLP training for $600. Training Ctr-Danvers, MA. Quality—very poor No formal phone support agreement. Message ctr. No information None 486 4MB D0S-foreground background 120 MB minimum Epson-Dot Matrix VGA Color Optional NIST, Toxicology, Forensics, Pesticides Formaster 19K and up Included 90 days $10,667 18% Included with hardware contract $136 /he 4 he min. 5-day operator trai at Finn, Institute at Cinn. OH. $1,995/course Electronic bulletin board for users. Technical phone assistance during war- ranty and for contracts. HP Internal Use Only Company ConfidentialVarian Saturn i ] Shimadzu OP 2000 Sawn ir Continuous dynade Continuous dynode SEM (Cu/Be} electron multiplier No information No information No information None None DIP optional Compaq 386 386 based DEC | 308 25 MHz No information 1 MB expandable 8 512KB main memory 3MB DOS-foreground/ 08 foreground/ Homemade background background Single-Tasking 40-10MB 112 MB IDE drive 100 MB 170 MB SCSI drive | Epson-Dot Matrix Okidata 320 300 dpi laser printer VGA Color VGA Color 1° high esoluion color Optional No information Not available NIST, Toxicology | nist wichemicat Requires optional PC for structures search NIST, NIH, EPA CLP like forms called Optional through Finnigan | None, requires optional EnviroPro PC for quantitation ‘$80K-$90K $54K-24K ‘60K Included Included No information 90 days | sodays No information $7,500 No information No information 9% No information No information ‘No information No information No information ‘158/hr + parts and 24 hr | No information No information response 5-day operstor training | No information No information at various locations. $1,800/course 1-800-# for technical No information No information applications, hardware and service assistance. 35 HP Internal Use Only Company ConfidentialRetrofits Customers will be able to take advantage of the enhancements to improve the sensitivity of their existing HP 5890/5971 by retrofit- ting parts. You should inform them that the parts should improve sensitivity but we cannot guarantee how much. We will NOT offer an upgrade from an HP 5971A to a full HP 5972. To inerease the full scan sensitivity of an existing HP 5971A order the following parts and follow the procedures in the following application note: MS 92-4 entitled “Improved scan sensitivity of the HP 59714 MSD” by Pat Perkins (23) 5091-5598E. Other relevant notes include: MS 92-5 entitled “Improving the sensitivity of your GC/MS system with electronic pressure control” by Linda Doherty (23) 5091-5493E. MS 92-3 entitled “Optimizing splitless injections on your GC for high performance MS analysis” by Linda Doherty (23) 5091-4587E. Part Needed Part Number Low bleed injection port septum (pack of 25) 5191-3383 or Merlin Microseal 5181-8816 Pesticide grade inj. port liner, wideactivated glass wool plug 5062-3587 30m x 0.25mm x 0.25um HP-5 column 190918-433, Rough Pump Oil 6040-0798 Diffusion Pump Oil 6040-0809 Electron Multiplier 05971-80102 Maximum sensitivity autotune see note below Note: The maximum sensitivity autotune can be obtained via CompuServe for users with G1034B MS ChemStation (DOS series) software or by upgrading the software to HP G1034C MS ChemStation (DOS Series) software or MS ChemSystem (HPUX) software (HP 59944B version B.07, or 59944C version C.02). Quote approximately 2 hours CE time. 37 HP Internal Use Only Company ConfidentialMarcom promotions Item Brochure Press Release Magazine Advertisement Peak Article Ton Notes Article Sales Training Manual Ordering Guide Specification Sheet Application Notes a. Sensitivity b. Lock-out specs Product Support Plan Hardware Manual APG Newsletter Article Magazine Article 38 Owner SID Marcom SID Mareom SID Marcom SID Marketing SID Marketing ‘SID Marketing/Marcom SID Marketing/Marcom SID Marketing/Marcom SID Marketing/Marcom ‘SID Marketing/Marcom SID Marketing/Marcom SID Product Support SID Marcom SID Marketing SID Marketing Dat Dee. Nov. Dee. Feb. Dee. Dee. Dee. Dee. Dee. Dee. Jan. ie 1, 1992 1, 1992 1, 1992 1, 1992 15, 1992 1, 1992 15, 1992 15, 1992 1, 1992 1, 1992 1, 1992 Mar. 1, 1993 Mar. 1, 1993 Nov. 1, 1992, Dec. 1, 1992 HP Internal Use Only Company ConfidentialOverview Support strategy Installation strategy Support Since the HP 5972A is an evolutionary product the ramp up time for customers, AE, CE and FE training should be relatively short. GC/MS | training for CEs will include the HP 5972A beginning with the October, 1992 course. The complete product support plan will be written by Cris Abbott and will contain all the details. A site approval will not be required but the customer must provide the correct electrical and space requirements as specified in the product support plan. Guaranteed customer specification of 10:1 rms s/n on 10 pg of HCB will be performed on-site. ‘HP 59724, #060 HP 599404, HP 599404, HP G1030A 39 ‘Mass Selective Detector ‘MSD-IRD Interface HP-UX ChemStation + 59944B HP-UX ChemStation + 59944C DOS ChemStation + G1034C 4.0 hours 1.0 hours 18 hours 28 hours 11 hours HP Internal Use Only Company ConfidentialConclusion In summary, we want you to leave the customer with the knowl- edge that the HP benchtop GC/MS system is highly distinguishable from the competition in the following areas: 1. HP offers “state of the art” proven GC/MS system technology. 2. HP offers the ultimate quantitative GC/MS system with unex- celled linearity, ion ratio stability, reliability, reproducibility and target compound software. 3. The HP 5972A offers competitive scan sensitivity and the best SIM sensitivity of any benchtop mass spectrometer. 4. HP will be there for the long term with the best service and support offered by any vendor. We also provide true growth paths by using industry standard software running on DOS and HPUX. that can be connected through ChemLAN. 5. HP offers tools for getting the customer up and running quickly such as on-site training, CBT (computer based training), the MS maintenance and MS fundamentals tapes, ARCS at the Atlanta ‘Training Center and customer courses. All these add up to a TOTAL PERFORMANCE SOLUTION that the customer needs to be successful. 40 LEP Internal Use Only Company ConfidentialHP 5972A features, advantages and benefits at a glance Appendix General F: True classical EI and CI spectra A: Better isotope ratios; better reproducibility and ability to iden- tify trace components in complex matrices B: Improved high confidence defensible data that stand up to legal challenge and professional examination Universal and specific detection ‘A: Provides sensitive detection over almost the complete range of organic compounds a gas chromatographer will encounter B: Does the work of most other GC detectors High field reliability of benchtop GC/MS systems Lower downtime, more samples per day Low cost of ownership, saves money, higher income Responsive service Instrument uptime is increased Reliability for optimum lab productivity Single vendor solution for complete system Better serviceability and instrament uptime Reliability for optimum lab productivity F: Excellent training with a complete curriculum of MS courses taught by a large faculty of MS experts A: Enhances customer knowledge and expertise Greater efficiency and lab productivity F: True Total Jon mode of operation A: Universal detection and greater sensitivity for trace analysis B: Aids lab productivity F: Price for low cost DOS system bundle is less than $50K. A: Every lab can afford B: Lab can add MS to its portfolio of techniques Fi Mass range from 1.6-700 amu A: Can run higher MW compounds such as anabolic steroid deriva- tives B: Adds to lab application capabilities F: MS/RD option on DOS A: Confirmatory technique B: Adds to lab application capabilities, improved confidence in the answer 41 HP Internal Use Only Company ConfidentialHardware F: Short capillary direct interface ‘A: Better sensitivity and less sample degradation B: More reliable results at lower sample levels, better results on thermally sensitive samples F: New redesigned “state of the art” detector ‘A: Optimizes the ion optics while reducing noise B: Increased sensitivity, linearity, and lifetime F: EM Detector horn (dynode) can be inexpensively and easily replaced ‘A: Replacement time decreased : Greater uptime and productivity : Redesigned vacuum manifold and o-ring ‘A: Reduced surface area exposed to vacuum, lower background : Provides improved system reliability, better data ': New rough and diffusion pump oils ‘A: Reduced hydrocarbon background B: Higher sensitivity, better data F: Enhanced performance GC/MS kit ‘Az Includes new “low bleed” column, Merlin microseal septum and others B: System is optimized high performance GC/MS analysis F: New SmartCard ‘A: Increased buffer storage for enhanced operation with the multi- tasking data systems B: Tasks are executed faster, higher productivity F: New exterior cover with “pop off” feature A: Easy to access source :: Maintenance is facilitated New Edwards E2M2 rough pump ‘A: Improved pumping and less maintenance B: Greater uptime, higher reliability ': Electronic pressure control on the 5890 GC Series I ‘A: Automatically optimizes inlet performance by allowing the user ‘to control the carrier gas at a constant flow rate B: Higher sensitivity and reproducibility, better chromatography 42 HP Internal Use Only Company ConfidentialF: MS interface to GC is optimized for fused silica capillary columns A: Excellent chromatographic resolution B: Superior sensitivity and quantitation Software Computer operating software and hardware flexibility with DOS and HP-UX A: Allows customer a choice of data system platforms B: Data system fits the lab analysis needs and productivity requirements User friendly Computer Based Training Facilitates customer's learning curve Faster uptime and productivity F: New maximum sensitivity autotune A: Accomplishes a customized high sensitivity manual tune automatically B: Obtains maximum sensitivity, better data, higher productivity F: Open networking with powerful HP ChemLAN A: Allows networking to large number of instruments and data systems Bi True growth path for the lab F: Most complete automation A: Provides capability for running multiple samples unattended B: Cost and time savings F: Multitasking DOS and HP-UX software ‘A: Can perform several tasks at once : Efficient use of time which saves money F: Simple automatic and manual tuning for EI and Cl; special DFTPP and BFB autotunes for environmental analysis ‘A: Automatically tunes and calibrates the MS for general purpose El and CI operation B: Speeds setup, assures day-to-day reproducibility and eliminates the need for an operator skilled in tuning mass spectrometers F: Fast accurate library searching : HP offers NIST, Wiley, Pleger/Maurer/Weber Drug and the Stan Pesticide Libraries B: Allow the user to quickly and positively identify compounds by comparing your classical run spectra with recognized standard library spectra 43 HP Internal Use Only Company ConfidentialOption #201 ship kit Tower level parts Part Number Part Description Quantity (pin 05890-61455) 05890-90255 Septa instructions 1 1460-1914 Wireform 1 5181-8830 Column Nut 2 18740-20885 Gold Plated Seal 1 19091 S-433, 30m x.25mm x.254m Column 1 18081-90800 Label-Toll Free 1 19251-00100 Wrench CIP 1 19251-90150 Instruction Sheet Insert 1 19251-90775 Gold Seal Info 1 3150-0532 Moisture Trap 1 3150-0414 Oxygen Trap 1 5061-5869 Washer 375 0D 1 5181-3323, VespeVGraphite Ferrule 250 um ID 1 5180-4108, Nut 1/8" Brass 1 5180-4109 Front Ferrule V/8" Brass 1 5180-4115 Back Ferrule 1/8" Brass 1 5180-4181 O-rings 1 5180-4182 Viton o-tings 1 5180-4196 Copper Tubing 1 5181-3316 Single Taper Deactivated Liner 1 5062-3587 Single Taper Deactivated Liner w/Weol 1 5091-4587E GC/MS Optimization Procedure 1 5181-3383 ‘mm Thru-Hole Septa 1 5181-8816 Microseal Kit 1 15955-9022 Logbook 1 9300-0311 Leak Detector 1 9301-0713 Syringe 63 00 1 19245-40030 Syringe Plunger Button 1 5181-8896 Column Cutter 1 “4 HP Internal Use Only Company ConfidentialMaximum sensitivity autotune ‘The HP G1034C MS ChemStation (DOS series) software or the MS ChemSystem (HPUX) software (HP 59944B version B.07, and HP 59944C version C.02) offer a new tune program that allows users to autotune their instrument for maximum sensitivity across the entire mass range. The net effect will be spectra that have an increase in signal of approximately 10 times at low mass, 8 times in the mid mass range, and no change in high mass sensitivity COMPARED TO THE ORIGINAL AUTOTUNE WITH THE SAME EM VOLTAGE. Since this new autotune inereases the sensitivity considerably at low masses, normal background spectra (i.e. water, COs, air) might look unusually large when compared to spectra from the original autotune. A recently pumped down GC/MS system will show this more than a stabilized system. Consistently high air or water even with the maximum sensitivity autotune indicates that diagnostics should be performed. Diagnosing air leaks and high background should still be done using the “Air and Water Check” in the Diagnostics menu of the “Diagnostics and Vacuum System Control” of the application software, What is DIFFERENT about the maximum sensitivity autotune? This tune is meant for users that require maximum sensitivity of their HP 5972A, and are not constrained by the use of specific target tunes (such as DFTPP) or 2% relative 502 amu requirements. This, tune differs from the original autotune in that it ramps the repeller voltage, uses 0.55 peak widths vs. 0.50, and ramps the entrance lens differently. Any users who currently manually tune their instru- ‘ments for maximum sensitivity will probably not see any increase in sensitivity with this autotune. Limited testing has shown that BFB criteria (used for environmental work) may be met with this auto- tune software. To PERFORM the maximum sensitivity autotune: Load the MS application software. Go into the top level and pull down the tune menu. Go into “Manual Tune” and pull down the “Tune” menu. You will see a new menu item “Maximum Sensitivity Autotune.” Double click on this menu item and when the tune is completed your instrument will be tuned for maximum sensitivity and the new tune values will be saved in the tune file named ATUNE.U. 45 HP Internal Use Only Company ConfidentiatTo obtain the maximum sensitivity improvement you may need to edit existing methods by increasing the EM voltage over the auto- tune value. For example: Standard autotune EMV = 1800V Existing method specified EMV = Autotune + 400V Resulting EMV used during the run = 2200V ‘Maximum sensitivity autotune EMV = 1500V Edit method to specify EMV = Autotune + 700V Resulting EMV used during the run = 2200V Notice the resulting EM voltages are identical. There may be some cases where running the EM voltage at a value identical to the original autotune voltage will overload the signal to the detector. This will cause you to get an “excessive signal level” error or corrupt spectra in data analysis. In this case lower the EM voltage by at least 100V and rerun the method. If necessary, continue lowering the EM voltage until you no longer get an “excessive signal level.” 46 LEP Internal Use Only Company ConfidentialHP 5972A standard spectra autotune Averages Eipsise 0.10 UP Internal Use Only Company ConfidentialHP 5972A maximum 1HPS972 Maximum Sensitivity Autotune-v3.0 sensitivity autotune Perr er e ce\HPoMEN 15972 ANIME 4 Repeller 27.28 | 26 Fllamene 6 HP Internal Use Only Company ConfidentialHEWLETT PACKARD Scienitic instruments Division HP 5972A Mass Selective Detector ‘The HP 5972A Mass Selective Detector (MSD™) is a standalone capillary GC detector designed for use with the HP 5890 Series I! Gas Chromatograph. It is compact and transportable, requiring no cooling water or compressed air. This MSD™ includes the GC interface, high efficiency electron impact ion source, monolithic hyperbolic quartz quadrupole ‘mass filter, quick-change electron multiplier, drive electronics with a second generation on-board com: puter SmartCard™, and a high-reliability vacuum system, Hardware features Analyzer: = High efficiency electron impact ion source that features two long-life filaments for maximum lab productivity (CT ion source is also available as an accessory) '= Monolithic hyperbolic quartz quadrupole for superior resolution and stability 1 Long-life electron multiplier with snap-in quick change horn ‘Vacuum system: «= High reliabilty 60 Ls diffusion pump ‘ Custom vacuum manifold with o-ring seal for low background contamination #2 CFM rough pump with automatic vacuum protection during power failures 1 Super-refined SANTOVAC 5 diffusion pump fluid and low vapor pressure INLAND 45 rough pump fluid for reduced hydrocarbon background Gener: = Basy-access top cover and status lights = Temperature controlled GC and IRD interfaces to ensure sample integrity ‘= Computer controlled from either HP G1030A ‘ChemStation (DOS Series) or HP 59940A (ChemSystem (HP-UX Series) = New internal HP-IB MS control SmartCard™ provides increased data buffer storage for ‘enhanced operation with the DOS and HP-UX multitasking data systems ‘= Computer controlled calibration valve for easy, sutomated tuning Software features ‘= Programs for Tuning, Data Acquisition, Data Retrieval, Reporting, Quantitation, and Libraries Searches, 1 Application specific Autotunes™ for quick optimi- zation of MSD performance ‘= Optional software includes application specific packages for environmental and drug analysis, Specifications Sensitivity: Conditions for Hexachlorobenzene in full scan and ‘SIM with 30m x0.25 mm x0.25um HP-5 low bleed column (p/n 190918-433), Inj|Det 250°C, Oven pram 70°C for 1.5 min, 25°C/min to 275°C hold 2 ‘min, Total time = 11.7 min EMV = max sens tune +4400, col. pressure = 15 psi, solvent delay 6 min, threshold = 0, 243 (1.7 seans /see), rep max = 35V, peak width = 0.55 amu 1 Full Scan Sensitivity —Blectron Impact Ionization splitless injection, 10:1 s/n rms for 10 pg Hexachlorobenzene m/z 283.8 + 0.3, 50-300 amu 1 Selected Jon Monitoring—Electron Impact Ioniza- tion splitless injection, 10:1 s/n rms for 200 fz Hexachlorobenzene m/z 283.8 + 0.3, 500 msec dwell time, low resolution = Full Scan Sensitivity—Chemical Ionization splitless injection, 10:1 s/n rms for 20 pg Benzophenone m/z 183.1 + 0.3 amu using methane, 80-230 amu Other parameters: ‘= Maximum Sean Speed: 1800 amu/see, 0.1 amu assignment steps = Mass Range: 1.6-700 amu in 0.1 amu steps = Resolution: unit mass resolution = SIM Mode: DOS 50 groups with up to 30 masses/group HP-UX 200 groups with up to 20 masses/group = SIM Dwell Time: DOS 10 msec to 9,999 msec (approx. 10 see) HP-UX 10 msec to 9,999 msec (approx. 10 sec) = Dynamic Range: Calibration linear over 4 orders of magnitude = Total ADC Dynamic Range: 10° = Mass Axis Stability: + 0.15 amu over 12 hours of normal operation Physical specifications: = Height: 36 em (14 in) Width: 17 em (7 in) Depth: 65 em (26 in) = Weight: 23 kg (50 Ibs) mainframe 43 kg (84 Ibs) mainframe plus forepump ‘= Heat Dissipation: 2400 BTU*hr : 3000 BTU/hr including transfer line = Temperature: operating environment 15 to 35°C. = Humidity (non-condensing): operating 25-50% RH, non-operating 10-95% RH 49 Company Confidential, Subject to Change Without Note —10992Team members —— ‘The HP 5972A Team includes the following individuals from manu- facturing, marketing, product support and R&D. Cris Abbott Roy Anderson Kathy Arnold Yang Bao Mitch Barham Jamie Bartels Jim Bertsch Ernie Bonelli Tim Borrego Gerda Cerna Frank Cesarz Tom Christensen Pam Cotter Erika Crockett Linda Doherty Doug Durham Kim Felt David Fisher Mark Fisher John Fjeldsted Bill Frazer David Fulmer Mark Gerber Ed Guthrie doe Harland Kent Henry Lee Dan Hoey 50 dim Jacobsen Reith Knauss Dick Kolloff Irene Lee ‘Stephen Lee Craig Love Doug Melntyre Loyal Mealer George Melchiorsen Heidi Norderer Pat Perkins Gene Peterson ‘Susan Peters Terry Petralia Rich Phillips Carl Pieciotto Tor Prather Julie Roh Randy Roushall Bill Russ Jim Steiner June Tsai Lori Tulley dim Vanides Hansen Wat Ron Wellman HP Internal Use Only Company ConfidentialCompany Confidential HEWLETT PACKARD Information, descriptions and specifi publication are Subject to change without notice. Printed in USA. 1292 (23) 5091-6074EUS