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Applications and Uncertainties Associated with Measurements Using Fourier Transform Infrared Spectrometry, Gas Chromatography-Mass Spectrometry and Selective Ion Electrode Method in Fire Suppression Tests
IRC-IR-745
Liu, Z.G.; Su, J.Z.; Kim, A.K.; KanabusKaminska, J.M.; Lusztyk, E.

June 1997

ABSTRACT During full-scale fire suppression tests conducted at the National Fire Laboratory of the National Research Council Canada, Fourier Transform Infrared (FTIR) Spectroscopy, Gas Chromatography-Mass Spectrometry (GC/MS) and Specific Ion Electrode (SIE) method were employed to monitor the concentrations of the gaseous suppression agents in the test compartment. Also, these methods were used to determine the halogen acid gases generated during the fire suppression process. This report describes the application of these three analytical methods for a series of tests conducted with HCFC Blend A.. The results for the measurements of gaseous agent and halogen acid gas concentrations using these three methods are provided. The uncertainties associated with measurements using these three techniques are analyzed in detail. It is shown that FTIR Spectroscopy provides an instantaneous and continuous method for the measurement of multiple chemical species in the fire tests with reasonable accuracy. The GC/MS and the SIE methods involve periodical sampling and off-line measurements. Uncertainties associated with measurements using these analytical techniques are strongly dependent on the characteristics of the analytical methods themselves, the set-up of the sampling system, calibration procedure, sampling procedure, quantitative analysis and testing conditions. Considerable care is required to obtain accurate measurements in the presence of halogen acid gases.

TABLE OF CONTENTS ABSTRACT TABLE OF CONTENTS NOMENCLATURE 1.0 2.0 2.1 2.2 2.3 2.4 2.5 INTRODUCTION TEST FACILITIES AND PROCEDURES Fire Suppression Agents Test Room Fire Scenarios Experimental Set-Up Test Instruments 2.5.1 Fourier Transform Infrared (FTIR) Spectroscopy 2.5.1.1 Calibration of the FTIR Spectroscopy 2.5.1.2 Sampling and Analyzing Procedure of FTIR Spectroscopy 2.5.2 Gas Chromatography-Mass Spectrometry (GC/MS) 2.5.2.1 Calibration of GC/MS 2.5.2.2 Sampling and Analyzing Procedure of GC/MS 2.5.3 Selective Ion Electrode (SIE) System 2.5.3.1 Calibration of SIE 2.5.3.2 Sampling and Analyzing Procedure of SIE 2.6 Test Procedure 3.0 TEST RESULTS 4.0 UNCERTAINTIES ANALYSIS 4.1 Uncertainties in the FTIR Spectroscopy 4.2 Uncertainties in GC/MS 4.3 Uncertainties in SIE System 5.0 SUMMARY REFERENCES Appendix 1: HCFC Blend A Concentrations Measured by GC/MS Appendix 2: F- and Cl- anion Concentrations Measured by SIE System I II IV 1 2 2 2 2 2 3 3 3 4 4 4 4 5 5 5 6 7 9 9 10 11 13 14

II

NOMENCLATURE FTIR Fourier Transform Infrared GC/MS Gas Chromatography-Mass Spectrometry HAPE Halon Alternative Performance Evaluation HCFC hydrochlorofluorocarbon HCl hydrogen chloride HF hydrogen fluoride TDP thermal decomposition products SIE Selective Ion Electrode

III

1.

INTRODUCTION

Increasing concerns about the environmental consequences of the utilization of chemical fire suppression agents have recently prompted worldwide efforts to develop and evaluate environmentally-friendly replacements for Halon 1301 and Halon 1211 [1 - 5]. An ideal halon replacement for total flooding applications should meet these important criteria: high fire suppression effectiveness, low direct and by-product toxicity, zero ozone depletion and short atmospheric lifetime. Various analytical techniques are being used to evaluate whether halon replacements meet such criteria or not [6]. In full-scale fire tests for the Halon Alternatives Performance Evaluation (HAPE) project conducted at the National Fire Laboratory, the National Research Council Canada, Fourier Transform Infrared (FTIR) Spectroscopy, Gas Chromatography-Mass Spectrometry (GC/MS) and Selective Ion Electrode (SIE) method were used to monitor the concentrations of the agents used for fire suppression and to determine the combustion by-products generated during fire suppression [7]. Good results were obtained using these analytical methods. However, the test results indicated that there were some uncertainties associated with the measurements obtained using these test methods. Although these methods are often used in fire tests, no literature is available that discusses in detail the uncertainties associated with measurements obtained using these analytical methods. Previous research [8 - 11] reported that some difficulties exist when measuring combustion by-products in fire suppression tests, because of the severe testing conditions and probable contamination and/or loss of samples during the measurements. Dierdorf et al. [12] discussed the advantages and disadvantages of three measuring modes using a FTIR to determine combustion by-products in fire suppression test. Bulien [13] described the application of a FTIR spectrometer for measuring toxic smoke components in fire test. He indicated that missing information and details in calibration routines could lead to differences in results obtained using a FTIR spectrometer. This work describes the application of the FTIR, GC/MS and SIE methods in fullscale fire tests. The results of the measurements of the agent and the halogen acid gas concentrations using these three methods in Phase I of the HAPE project are compared. The uncertainties associated with measurements using these techniques are then analyzed in detail. The FTIR Spectroscopy provides an instantaneous and continuous method for the measurement of multiple chemical species during the fire tests. The GC/MS and the SIE methods involve periodic sampling and off-line measurements. Uncertainties related to measurements obtained using these techniques are strongly dependent on the characteristics of the methods themselves, the set-up of the sampling system, calibration, sampling procedure, quantitative analysis and testing conditions.

2.0 2.1

TEST FACILITIES AND PROCEDURE Fire Suppression Agents

In Phase 1 of the HAPE project, HCFC Blend A was evaluated as a potential replacement for Halon-1301 [7]. HCFC Blend A is a mixture of halogenated hydrocarbons with 82% HCFC-22 (CHClF2), 9.5% HCFC-124 (C2HClF2), and 4.75% HCFC-123 (C2HCl2F3). The remaining 3.75% is a de-toxifying agent, lemonene, that gives the agent its characteristic odour. The design agent concentration for fire extinguishment and thermal decomposition products (mainly HF and HCl) generated during fire suppression were examined in full-scale fire tests. As shown in Table 1, the thirteen tests conducted in Phase 1 of the HAPE project involved a wide range of agent concentrations (8.6 - 14.7%), nozzle design, discharge manifold and fire scenarios. 2.2 Test Room

A 121 m3 compartment, similar to Radar Room No.2 on the Navys Halifax Class frigates, was constructed inside the Burn Hall of the National Fire Laboratory. The test room is shown in Figure 1. It has a steel access door, three viewing windows and a pressure relief vent near the floor of the South wall. 2.3 Fire Scenarios

Test fires in Phase 1 of the HAPE project included eight tell-tale (TT) fires, three 50 kW square-pan (SP) fires and one 400 kW round-pan (RP) fire. The fire scenarios used for tests are given in Table 1. Heptane was used as the fuel for the tell-tale, squarepan and round-pan fires. Their locations in the compartment are indicated in Figure 1. 2.4 Experimental Set-Up

The mass loss rate of the agent as it discharged from the cylinder was measured by a weight scale with a digital readout. Thermocouples were placed at each fire location to determine the extinguishing time. Three thermocouple trees were set up in different locations of the compartment to measure room temperatures (see Figure 1). Three quartz ports connected to stainless steel sampling lines were placed at the same locations as the thermocouple trees. The sampling ports were arranged at different elevations to measure the distribution of the agent in the compartment. The elevation of these ports is indicated in Figure 1. As shown in Figure 2, the sample gases in the compartment were sampled continuously using three sampling quartz ports. The samples were filtered with microfiber filters in the sampling lines. A switching system, using solenoid valves, connected the FTIR to the gas-sampling lines from each of the three locations at 30 second intervals.

The sampling port for the collection of samples for measurement using GC/MS was located after the FTIR cell. These samples were used to determine the concentration of volatile organic compositions. Secondary, samples were obtained for analysis using SIE method. These samples were obtained using a 6 meter length of sampling line connected to the GC/MS sampling port (see Figure 2). The SIE method was used to determine acid gas concentration. All the sampling lines from the sampling ports in the room to the gas cell of the FTIR and the sampling port of the GC/MS were heated and maintained at the temperature of 155oC. This prevented the condensation of sample gases in the sampling line. The sampling line from the GC/MS sampling port to the SIE sampling port was not heated. All sampling lines were pumped continuously prior to the test and after the test to ensure clean gas samples. 2.5 Test Instruments 2.5.1 Fourier Transform Infrared (FTIR) Spectroscopy The FTIR spectroscopic method is based on the combination of an interferometer, usually of the Michelson type, with a sensitive infrared detector and a computer [14 - 17]. FTIR spectroscopy provides sensitive and very fast measurements with high resolution over a wide frequency range for the identification of a broad range of chemical compounds. In the HAPE project, a BioRad FTS 175 FTIR spectrometer was used online to measure the concentrations of the agent and its thermal decomposition products during full-scale fire tests. 2.5.1.1 Calibration of the FTIR Spectroscopy The calibration of the FTIR spectrometer for the agent, HCFC Blend A, was carried out by using commercial calibration gases for the three major components of the agent. The concentrations of HCFC-22, HCFC-123 and HCFC-124 used in the calibration mixture were 7.50%, 0.49% and 0.4%, respectively, which was the same as used in HCFC Blend A. Each HCFC component has a characteristic infrared absorption peaks. For HCFC-22, three infrared absorption peaks centered at frequencies of 3,025, 2,213 and 596 cm-1 , were selected as the reference. For components HCFC-123 and HCFC-124, the peaks centered at the frequencies of 697 and 672 cm-1 were used as references, respectively. Commercial HF samples, with concentrations of 970, 5339, 11,400 and 75,000 ppm, were used for calibration. HF has a unique absorption band in the frequency region of 3,600 to 4,300 cm-1 with approximately 10 to 18 sharp absorption peaks. The eight HF peaks at 3,788.9, 3,878.4, 3,921.0, 4,001.7, 4,039.7, 4,076.0 and 4,110.7 cm-1 were selected as references for HF. During each fire test, the HF concentration at a given time was determined by averaging the values corresponding to the eight peaks.

The calibration of the FTIR spectrometer for HCl was carried out using 500 and 75,000 ppm commercial samples. More than 16 HCl absorption peaks were found in its characteristic frequency region of 2,600 to 3,100 cm-1. The peaks in the P-branch at 2,776, 2,799, 2,822 and 2,844 cm-1 were selected as the HCl references. In each fire test, the HCl concentration at a given time was determined by averaging the values corresponding to the four peaks. 2.5.1.2 Sampling and Analyzing Procedures of FTIR Spectroscopy As shown in Figure 2, gas samples were drawn continuously from the compartment through three gas-sampling lines to the FTIR spectrometer. The gas sample from each sampling location was analyzed for 30 second using switching valve system. An infrared (FTIR) spectrum over a wide frequency range of 400 to 4,500 cm-1 was collected from the sample gas. Measurement using the FTIR lasted more than 12 minutes for each test. Quantitative analysis of the agent and thermal decomposition products were obtained by comparing infrared absorption peaks from the fire tests with the corresponding reference peaks obtained using the calibration gases. 2.5.2 Gas Chromatography-Mass Spectrometry (GC/MS) Gas Chromatography-Mass Spectrometry (GC/MS) is the combination of the chromatographic technique with mass spectrometry: full use is made of the separating power of GC together with the structural information derivable from MS [18 - 20]. In the HAPE project, a Model 5995 Hewlett/Packard Gas Chromatography/Mass Spectrometer was used to measure the concentration of the agents used and other components present in the test room. 2.5.2.1 Calibration of GC/MS Several commercial single component gases were used to calibrate the GC/MS. The concentrations of HCFC-22, HCFC-123 and HCFC-124 components used for the GC/MS calibration were the same as those used in the FTIR calibration (7.50%, 0.49% and 0.4%, respectively). The single component standards were sampled using an air-tight syringe from a decompressed free-flowing stream. Various volumes of calibration gases were then loaded on the sorption tubes. An Envirochem Model 810 A with two stage thermal desorber/concentrator was used to thermally desorb and concentrate the volatile component prior to analysis in the GC/MS. The volatile constituents were then separated in the capillary columns and analyzed by the MS detector. The corresponding ion spectrum for each component was compared with the NBS75 spectral library with the aid of a computer. Their peaks were identified and quantified as MS counts. Volume normalized MS area for each component

was then plotted against the tube load. experimental points for each component: Ci = Ai + Bi X

A linear equation was fitted through the

(1)

where Ci is the concentration of ith component [ppm], Ai and Bi are response factors of ith component respectively and X is the normalized MS response [cts/mL]. 2.5.2.2 Sampling and Analyzing Procedures of GC/MS The GC/MS was not conducted on-line. The measurement using the GC/MS involved: preparing sorption tubes, sampling, transporting and storing samples, and analyzing samples in the laboratory. In Phase 1 of the HAPE project, three types of sorption tube (Carbotrap and Carbotrap tubes and Standard Three Layer Glass Beads-Teenax-Ambersorb tubes) were used. Prior to the test, the sampling tubes were cleaned by purging with ultra pure helium for 10 to 15 minutes while they were heated to a temperature of 2500C. As shown in Figure 2, the sampling port for GC/MS was located after the FTIR cell and consisted of a SS-Tee that was equipped with a teflonized septum under a SwageLok Fitting. During the test, the gases from the test room were sampled manually with a gas-tight high precision syringe (Hamilton 1 mL). The contents of the syringe were then injected in a stream of laboratory air into a sorption tube. The tube was later stored in a screw capped glass sheath. At the end of the test, the exposed sorption tubes were transported to the GC/MS facility where they were thermally desorbed and analyzed. The components of the sample gas were identified with the aid of a HP supplied 75,000 compound library with a probability matching algorithm and three other libraries [21]. Quantitative analysis of the agent concentrations was obtained by using equation (1) and comparing the peaks recorded from the fire tests with the corresponding reference peaks produced using the calibration gases. 2.5.3 Selective Ion Electrode System Thermal decomposition products, including hydrogen fluoride (HF) and hydrogen chloride (HCl), were produced in the fire suppression process due to the interactions between the agent and the flame. In Phase 1 of the HAPE project, the thermal decomposition products were collected by Wet Chemistry and then analyzed using a Selective Ion Electrodes (SIE) method. 2.5.3.1 Calibration of SIE System Orion solid state Selective Ion Electrodes were used to determine the concentrations of HF and HCl acid gases produced during the fire suppression process by

analyzing the levels of F- and Cl- anions in a solution prepared using the gas samples [22, 23]. Each Selective Ion Electrode system was calibrated using calibration standards prepared from 0.1 N Acculute solutions of NaCl and NaF using the Incremental Technique method. A semi-logarithmic plot of each electrode potential versus halide ion concentration was constructed. A calibration curve was fitted to more than 30 calibration points to provide the appropriate response factor equation. For calibration, the concentrations for F- and Cl- anions were varied from 0.0 to 8.0 and 0.0 to 40.0 mmol/L, respectively. 2.5.3.2 Sampling and Analyzing Procedures of SIE System As shown in Figure 2, the sampling port for Wet Chemistry using a SS-Tee was located at the exit of the cold exhaust line. An all-glass threaded Supelco Midget bubbler equipped with a gas frit diffuser to increase the gas/liquid contact surfaces. 22 mL screwcap vials were used as collection vessels. The collection vessels were prefilled with 10 mL of 0.1 N NaOH solution prepared using an Anachemia Acculute Standard Volumetric Solution. The gases were sampled through the vials at a volumetric flow rate of 100-200 mL/min for 90-120 seconds. The mass transfer between the gas stream and the solution occurred in irreversible chemisorption-neutralization reactions. The gaseous hydrogen fluoride (HF) and chloride (HCl) were then trapped from the sampling gases and dissolved in the hydroxide solution while most other components in the sample remained undissolved. In the laboratory, the pH of the solution in each vial was adjusted with a small volume of concentrated sulphuric acid. An aliquot of the exposed solution was then adjusted using TISAB II solution. A Fluoride Selective Electrode was used to determine the concentration of F- anion. Another aliquot of the exposed solution was adjusted using an ISA buffer and a Chloride Selective Electrode was used to determine the concentration of Cl- anion. The quantitative analysis of the F- and Cl- anions concentrations were obtained by comparing the electrode potentials of the fire gases with the corresponding calibration curves produced using the standard solutions. 2.6 Test Procedure

Computers controlling the data acquisition system and the FTIR were started simultaneously at time zero. Test fires were allowed at least a 30 s pre-burn. During the pre-burn period, the door of the compartment was kept open. Agent discharge was activated manually at 60 s and lasted about 10 s. The pressure relief vent and the access door were deliberately held closed during the tests. The tests were terminated after 10 minutes. The pressure relief vent was then opened and a fan connected through an exhaust duct was activated to ventilate the room.

3.0

TEST RESULTS

The FTIR and GC/MS were used to measure the agent concentrations and the FTIR and SIE were used to measure the acid gases generated during the fire suppression process. Agent Concentrations As shown in Table 1, Test H-1 was a dump test, without any fire, to determine the agent discharge time and its concentration in the room. Test H-12 was a fire test without any extinguishing agent used. These two tests are not discussed in the present work. In Tests H-2 to H-6, the door was opened for a moment to relieve some of the pressure during the discharge. For all subsequent tests, both the louvers of the pressure relief vent opening and the door were kept closed during the discharge. The filters in the sample lines are designed to remove most of the particles from the sampling gases. The filters must be changed prior to every test. However, the filters in the sampling lines were not changed until Test H-7 in Phase 1 of the HAPE project. As a result, the filters in the sampling lines were clogged during Tests H-2 to H-6. The clogged filters affected the measuring accuracy of FTIR, GC/MS and SIE. After Test H7, the filters were changed prior to every test. The agent concentrations measured by GC/MS in Phase 1 of the HAPE project are listed in Appendix 1. The agent concentrations measured by FTIR are shown in Figure 3 (for Tests H-2, H-3 and H-7 to H-13). The agent concentrations measured by GC/MS in the corresponding tests were plotted in Figure 4. The FTIR spectroscopy method continuously records the changes of agent concentrations in the compartment from the beginning of the discharge. The agent concentration in the compartment quickly reached its design value and was distributed uniformly in the compartment shortly after the discharge. The agent concentrations measured by the FTIR from different sampling ports did not display any obvious fluctuation. For Test H-2, the target agent concentration in the room was 8.6%. The FTIR results showed that the maximum agent concentration actually reached 9% at the beginning of the test, then continuously dropped. For Test H-3, the agent concentrations as measured by FTIR were lower than the design value (8.6%), because the filter in the sampling lines was clogged during the test. After Test H-7, the agent leakage from the room was minimized during the discharge by closing both the door and the louvers of the pressure relief vent. The filters in the sample lines were also changed for every test. As a result, the agent concentration in the compartment did not drop after the discharge and the agent concentrations measured by the FTIR were very close to the target concentration. The target concentration in Test H-7 was 9.3% and the average agent concentration measured by the FTIR was 9.2%.

The number of points measured by GC/MS method for in full scale fire tests was limited. In Test H-8, only four GC/MS data points were obtained in a testing period of nearly 400 seconds, in comparison with 180 data points obtained using the FTIR method. Also with the switching system, the gases from some sampling lines were missed during the sampling process for GC/MS. The agent concentrations measured by GC/MS showed significant fluctuations from one testing point to another, as shown in Figure 4. The measured values obtained using the GC/MS method were lower than the target concentrations as well as the values measured by FTIR. In Test H-11, the average agent concentration measured by GC/MS for a testing period of nearly 400 seconds was 5.58% compared with the design concentration of 8.6%. Thermal Decomposition Products (TDP) Thermal decomposition products generated during the fire tests are strongly dependent on the size of the fire and the agent concentration used for suppression. The HF and HCl concentrations measured by SIE in Phase 1 of the HAPE project are listed in Appendix 2. HF and HCl concentrations measured by FTIR and SIE methods are shown in Figures 5, 6 and 7. The FTIR spectroscopy continuously recorded the formation of halogen acid gases in fire suppression from the beginning of the discharge. In Test H-2, eight tell-tale fires were employed but not extinguished. The FTIR results show that only a small amount of halogen acid gases were produced in the test with relatively small fires. With the increase in the fire sizes (e.g. 200 kW in Tests H-3 and H-8), very high concentrations of halogen acid gases were produced, when the fires were not extinguished. However, when the agent concentration was increased to 14.7% in Test H-10, Figure 7 shows that only a small amount of HF and HCl acid gases were produced as the fire was quickly extinguished. When the fires were reignited at 680 s in Test H-10, after an agent concentration had decreased due to the operation of the exhaust fan, a significant amount of halogen acid gases were produced. The FTIR data in Figures 5 and 6 shows that HF and HCl concentrations measured in Test H-3 were lower than those measured in Test H-8 under the same fire scenarios. This indicates that the clogged filters in Test H-3 resulted in an underestimation of the production of halogen acid gases during the fire suppression process. In some unextinguished tests (e.g. H-8, H-9 and H-13), HF concentrations measured by FTIR displayed significant fluctuation from one sampling port to another, although the agent was distributed uniformly in the test room. This is because the formation of halogen acid gases varied depending on the local temperature. In Test H-8, sampling port 3 was close to the ceiling of the room where the local gas temperature was high. Sampling ports 1 and 2 were located at low elevations close to the floor, where the local gas temperature was relatively low. Hence, halogen acid gases measured at sample port 3 were higher than those measured at the other two ports.

In comparison with the measurements using the FTIR, the acid gases measured by the Wet Chemistry method were integrative samples from three sample points and represented a time and space-averaging of the concentrations in the test room. The results shown in Figure 6 for Tests H-8, H-9 and H-13 indicated that HF and HCl concentrations measured by the Selective Ion Electrode System were much lower than those measured by the FTIR spectroscopy. This suggests that some of the acid gases were lost in the sampling systems. In Test H-10, HF and HCl concentrations measured by the Selective Ion Electrode System were much higher than the concentration measured by the FTIR and had almost the same levels as measured in Tests H-9 and H-13 in which the fires were not extinguished. This was not true for the case where the fire was quickly extinguished. In this test, the sampling system for the Wet Chemistry method were probably contaminated when the sample gases flowed through a long and cold stainless steel sampling line. 4.0 UNCERTAINTY ANALYSIS

Uncertainties generated from measuring agent concentrations and thermal decomposition products are strongly dependent on the characteristics of the analytical methods themselves, the set-up of the sampling system, calibration and sampling procedures and testing conditions. 4.1 Uncertainties in FTIR Spectroscopy Measurement The FTIR was used to continuously measure the components of the gases sampled from the test room. The uncertainties related to the measurements with the FTIR are due to the calibration, sampling and quantification of experimental signals of the FTIR. Uncertainties in the Calibration of the FTIR The uncertainties associated with the FTIR calibration can be attributed mainly to the impurity and concentration range of the calibration gas, and calibrated data points required to form a proper calibrating curve. For the calibration of the agent, the concentration of the agent was about 8.5% with a single-point calibration. This could cause some uncertainties in some tests as the agent concentrations were higher than the calibrated concentration. For the calibration of HF, commercial samples with four HF acid concentrations were used to construct a proper calibration curve. For the calibration of HCl, however, commercial samples with only two HCl acid concentrations were employed to produce a calibration curve. During the full-scale fire tests, a large amount of acid gases were produced in the unextinguished fires. The calibration ranges for the halogen acid gases covered the concentrations of HF and HCl acid gases produced in the tests. However, the increase in the acid gas concentration is not linearly [2]. As a result, the limited numbers

of calibration points used for HCl could result in some uncertainties in the measurement of acid gases. Uncertainties in the Test of the FTIR The measurement using FTIR spectroscopy in the HAPE project was the external absorption mode. The gas samples were withdrawn through the metal sampling line and measured at the outside of the test room. The filters in the sample lines could result in some uncertainties in the measurements as the filters were clogged in some tests. Also, the particles retained by the filter, which were highly absorbent and reactive, could also prevent a fraction of the halogen acid gases reaching the FTIR for analysis. As shown in Figures 3 and 5, the concentrations of the agent and halogen acid gases measured by the FTIR in Test H-3 were significantly lower than those without the clogged filters in the later test. Also, the acid gases are very reactive and, even though stainless steel sampling lines were heated, the interaction between the reactive acid components and metal tubes occurred, resulting in losses of sampling acid gases and increased the uncertainties in the measurements. Uncertainties in the Quantitative Analysis of the FTIR Since multiple chemical compounds were produced in the fire tests, there were overlaps of the FTIR signals in some analysis regions. The signal noise could lead to ambiguous determination of the exact height and area of some absorption peaks for the analysis of the agent and acid gases. Hence, this could result in an underestimated or overestimated concentrations of the agent and halogen acid gases. It was estimated that for the cold discharge test, the uncertainties of the FTIR in measuring the agent concentration was less than 7%. For the fire tests, the uncertainties were within 13%, because of the increasing uncertainties due to interference from the decomposition products. The uncertainties of the FTIR in the measurement of HF and HCl concentrations were estimated about 20% higher than those for the measurement of the agent concentration [7]. 4.2 Uncertainties in GC/MS Measurement

The GC/MS analysis for the measurement of the agent concentrations was conducted off-line. The gases from the test room were sampled manually, put in storage, transported to the laboratory and then analyzed by GC/MS. Thus, the uncertainties produced in the measurement by GC/MS include not only those in the FTIR analysis, such as calibration and signal quantification uncertainty, but also those uncertainties related to the collection of the sample gas, and the storage and transport of the sample gas to the laboratory. Uncertainties in the Calibration of GC/MS

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As the same as discussed in the calibration of FTIR, the uncertainties related to the calibration of GC/MS were due to impurities of the calibration chemicals, to the calibration concentration and to the number of calibrated data points. The purity of chemicals used for calibration was usually very high (99%). The number of data points for the GC/MS calibration was also increased by diluting the calibration standards. However, the concentration of the calibration standard was still lower than some values used in the tests. This could result in some uncertainties in determining the agent concentration, when the agent concentration exceeded the calibrated range. Uncertainties in the Sampling Procedure of GC/MS There were two uncertainties arising from the sampling process for GC/MS analysis. The first uncertainty resulted from the sampling period as the sampling gas was quickly and manually drawn with a gas-tight syringe at the sample port. The second uncertainty in the GC/MS sampling process was associated with the retaining capabilities of the sorption tube. The gas samples were affected by the clogged filters, the non-uniform pumping cycles, the switch from one sample port to the other, and the fluctuation of the gas composition in the compartment during the short manual sampling period. The sampling volume of the gas-tight syringe also influences the sampling accuracy. In Test 6, the size of the gas-tight syringe was changed from 1 mL to 0.5 mL. As shown in Appendix 1, the agent concentrations measured by GC/MS in Test H-6 were significantly lower than those measured in the test in which samples were obtained using a 1 mL syringe. In Phase 1 of the HAPE project, three types of sorption tubes (Carbotrap , Carbotrap and the Standard Three Layer Glass Beads-Teenax-Ambersorb tubes) were used. As shown in Figure 8, the concentrations of HCFC-123 and HCFC-124 components in the agent measured by GC/MS did not fluctuate with the changes in sorption tubes used. But, the concentration of the HCFC-22 components changed from one sampling point to another. The test results also showed that the retaining capabilities of the Standard Glass Beads-Teenax-Ambersorb tubes was better than those of the other two types of sorption tube, but still resulted in an underestimation of the concentrations of HCFC Blend A in the tests. The retaining capabilities of sorption tubes were also affected by their age and the frequency of their utilization. Those sorption tubes with high utilization frequencies had lower retaining capabilities due to the deactivation of the sorption sites. In Phase 1 of the HAPE project, the age and utilization frequency of the sorption tubes were not identified. This lead to differences in the retaining capabilities of sorption tubes for samples, because different sorption tubes were used. The existence of halogen acid components in the sample gases can further reduce the retaining capabilities of the sorption tubes by damaging the beads of the sorption material. Uncertainties in Storage and Transport for GC/MS Analysis

11

The components of the agent HCFC Blend A are relatively stable. However, during storage and transport, the chemical interaction between the halogen acid components in the sample gases and the sorption material could damage the beads in the sorption tubes. This resulted in some uncertainties for the GC/MS analysis. Uncertainties in the Quantitative Analysis of GC/MS The uncertainties produced in the quantitative analysis using the GC/MS method are relatively small in comparison with those observed for the FTIR method. During quantitative analysis of the sample gases, the interference from other chemical compounds could be reduced to a low level by the proper separation of Gas Chromatography. Hence, the uncertainties in the measurements obtained using GC/MS are mainly due to the manual sampling procedure and the retaining capabilities of the sorption tubes. The existence of the halogen acid components in the sampling gases further increases the uncertainties in the GC/MS measurement. As a result, the agent concentrations measured by GC/MS are significantly lower than the target concentrations. The uncertainties related to the measurements with GC/MS are higher than those related to the measurements using FTIR spectroscopy. 4.3 Uncertainties in SIE Measurement

The Selective Ion Electrode (SIE) method for the measurement of halogen acid gases was also performed off-line. The sample gases were collected using Wet Chemistry and then analyzed by the Selective Ion Electrode System. The uncertainties associated with this analysis procedure include uncertainties in the collection and storage of the samples using the Wet Chemistry method, and uncertainties in the calibration and quantitative analysis of acid gases using the Selective Ion Electrode method. Uncertainties in the Collection and Storage of Sampling Gases Using Wet Chemistry For the HAPE project, heated stainless steel was used for the primary sampling lines. However, the sample line that connected the GC/MS sample port to the SIE sample port was not heated. Hence, the water vapour in the sampling gases could condense in the tube, and halogen acid components in the sampling gases could react with the metal tube in the presence of air and moisture during the test. The acid gases are very reactive with the stainless steel [24]. Sheinson et al. [8, 9] found that HF sampled using a short stainless steel tube showed significantly lower concentrations than when sampled using a Teflon tube. As shown in Figure 6, the results in the present tests also indicated that the concentrations of HF and HCl acid gases measured by SIE were significantly lower than those measured using the FTIR, indicating loses in the sampling procedure due to the interaction of the sample gases with the cold metal walls. Also, cold metal sample lines can contaminate samples if the same sampling system was repeatedly used in different tests. As shown in Figure 7, HF and HCl concentrations measured by Selective Ion Electrode System in Test H-10 were much higher than those values measured by FTIR, when the fire was quickly extinguished.

12

The effectiveness of the sampling procedure for the Wet Chemistry method was also affected by the collective efficiency of the bubbler vials and the flow rate of the sampling gases through the bubbler vials. The collective efficiency of bubbler vials was designed for a certain range of hydrogen halides concentrations. In the full-scale tests, a large amount of halogen acid gases was produced, when the fire was not extinguished by the suppression agent. The high concentrations of hydrogen halides produced during the fire suppression process in some cases exceeded the upper range for the vial and lead to premature saturation of the ion trapping solutions in the bubbler vial. Hence, halogen acid components in the sampling gases were not all collected by Wet Chemistry in some tests. The high volumetric flow rate of the sampling gases could also reduce the stripping of acid components from the gas stream if the contact time for the gas bubbles within the solution was too short. Great care was also needed to store and transport the acid gases to prevent unwanted reactions and loss, because of the reactivity of the acid gases. Uncertainties in the Calibration and Quantitative Analysis Using SIE For the calibration of the Selective Ion Electrode System, calibration standards prepared from Acculute solutions were used. The calibration curves were plotted based on more than 30 calibration points with a wide range of F- and Cl- anion concentrations. The uncertainties related to the calibration of the SIE, therefore, are relatively small. Other halogen components, such as COF2 and COFCl, were also produced during the fire suppression process and hydrolyzed rapidly in the presence of water. Hence, in quantitative analysis of the acid concentrations, F- and Cl- anions measured by Selective Ion Electrode System include F- and Cl- anions from both halogen acid gases and other components in the samples. As a result, the concentrations of the halogen acid components in the samples could be overestimated by the SIE method. The FTIR results showed that the amount of COF2 and other components generated during the fire suppression process was relatively small. These results indicated a 5 - 10% uncertainty in the HF and HCl measurement due to the presence of COF2 and other components in the sample gases. 5.0 SUMMARY

Fourier Transform Infrared (FTIR) Spectroscopy can provide an instantaneous and continuous method for the measurement of multiple chemical species in fire tests with reasonable accuracy. The uncertainties related to the measurements by FTIR are influenced by the calibration concentrations, the number of calibrated data points, the filters in the sampling lines and the signal interference in the quantitative analysis. The chemical interaction between the sample gases and metal sampling lines could further increase the FTIR uncertainties in the measurement of multiple chemical species.

13

Gas Chromatography-Mass Spectrometry (GC/MS) for the measurement of the agent concentration was conducted off-line. GC/MS cannot continuously record the changes in the agent concentrations in the test room. The number of measuring points is limited. The GC/MS method requires more elaborate calibration, and more timeconsuming and labour-intensive sampling procedure and quantitative analysis. For the GC/MS, the uncertainties produced from the calibration procedure and quantitative analysis are relatively small, in comparison with those in the FTIR method. However, the sampling procedures used to obtain samples for GC/MS analysis has a significant effect on the measuring accuracy. Also, the retaining capabilities of the sorption tubes have a significant effect. The existence of the halogen acid components in the sample gases can further increase the uncertainties of the measurements by GC/MS. The overall uncertainties in the measurement of the agent concentration by GC/MS are higher than those with the FTIR spectroscopy. For the GC/MS method, the collection efficiency for the sample gases must be systematically verified prior to the test. The Specific Ion Electrode (SIE) method for the measurement of halogen acid gases was also conducted off-line in the tests. The concentrations obtained with the SIE method are time and space-averaged. The uncertainties for this method are mainly due to chemical interactions between the acid gases and metal sampling lines. In addition, the improper design of the bubbler vials and flow rates in the sampling process also increases the uncertainties of the SIE measurement. The concentrations of F- and Cl- anions measured by the Specific Ion Electrode method are the sum of both halogen acid gases and other components (e.g. COF2) in sampling gases. REFERENCES 1. Grant, C.C., From the Halons of Yesterday to the Challenges of Tomorrow, Proceedings of Fire Safety -- Without Halon?, Zurich, Switzerland, September 7-9, 1994, pp. 7-39 Su, J.Z., Kim, A.K. and Mawhinney, J.R., Review of Total Flooding Gaseous Agents, J. of Fire Protection Engineering, vol.8, No.2, pp.45-64, 1996 Tapscott, R.E., Summary of Current Agents, Presented at 1994 International CFC and Halon Alternatives Conference, Washington, DC, U.S.A., 1994 Metchis, K., The Regulation of Halon and Halon Substitutes, Proceedings of Halon Options Technical Working Conference, Albuquerque, NM, USA., 1994 pp. 7-30 Kim, A.K., Su, J.Z., Mawhinney, J.R. and Kanabus-Kaminska, M., Full-Scale Fire Testing of HFC-227ea and HCFC Blend A, Proceedings of Halon Options Technical Working Conference, Albuquerque, NM, USA., 1996 Miller, T.L. and Green, A.E.S., A Survey of Techniques for Fire Suppressant Studies, Proceedings: Halon Alternatives Technical Working Conference 1994, PP.453-463. Mawhinney, J.R., Kim, A.K., Su., J.Z., Kanabus-Kaminska, M., Crampton, G., and Lusztyk, E., Report on Full-Scale Fire Testing of HCFC Blend A - ND Research Project HAPE 7665-1 (CFFM3-2), Client Report of National Fire

2. 3. 4.

5.

6.

7.

14

8.

9.

10.

11.

12.

13.

14. 15. 16.

17.

18. 19. 20. 21. 22. 23. 24.

Laboratory of the National Research Council Canada, 1995 Sheinson, R.S., Musick, J.K., and Carhart, H.W., HF and Hbr Production from Full-Scale CF3Br (Halon 1301) Fire Suppression Tests, J. of Fire and Flammability, Vol.12, P.229, 1981 Sheinson, R.S. and Alexander, J.I., HF and Hbr from Halon 1301 Extinguished Pan Fires, Fall Meeting, Eastern States Section Meeting/the Combustion Institute, Pittsburgh PA, 1982 Di Nenno, P.J., Forssell, E.W., Peatross, M.J., Wong, J.T., and Maynard, M., Evaluation of Alternative Agents for Halon 1301 in Total Flooding Fire Suppression Systems: Thermal Decomposition Product Testing, Proceeding: Halon Alternatives Technical Working Conference, Albuquerque, P. 162, 1993 Linteris, G.T., King, M.D., Liu, A., Womeldorf, C. and Hsin, Y.E., Acid Gas Production in Inhibited Diffusion Flames, Proceeding: Halon Alternatives Technical Working Conference, Albuquerque, P. 177, 1994 Dierdorf, D.S., Moore, T.A. and Skaggs, S.R., Decomposition Product Analysis During Intermediate-Scale (645 FT3) and Laboratory Scale (6.18 FT3) Testing of NFPA 2001 Agents, Proceeding: Halon Alternatives Technical Working Conference, Albuquerque, P. 177, 1993 Bulien, O. K., FTIR Spectrometer for Measuring Toxic Smoke Components in Fire Testing - Review of Equipment and Calibration Routines in NT FIRE 047, Fire and Materials, Vol. 20, PP.225-333, 1996 Smyth, M.R., Chemical Analysis in Complex Matrices, Ellis Horwood and Prentice Hall, England, 1992 Zyka, J., Instrumentation in Analytical Chemistry, Ellis Horwood and Prentice Hall, England, 1994 Ferraro, J.R. and Baslle, L.J., Fourier Transform Infrared Spectroscopy Techniques Using Fourier Transform Infrared, Vol. 3, Academic Press, New York, 1984 Ferraro, J.R. and Baslle, L.J., Fourier Transform Infrared Spectroscopy Applications to Chemical Systems, Vol. 1, Academic Press, New York, 1984 Pecsok, R.L. and Shields, L.D., Modern Methods of Chemical Analysis John Wiley & Sons, Inc., New York, 1968 Middleditch, B. S., Practical Mass Spectrometry, Plenum Press, New York, 1979 Ravindranath, B., Principles and Practice of Chromatography, Fllis Horwood Limited, New York, 1989 Bruno, T.J., Spectroscopic Library for Alternative Refrigeram Analysis, NIST Special Publication:794, 1991 Freiser, H., Ion-Selective Electrodes in Analytical Chemistry, Plenum Press, New York, 1978 Kenkel J., Analytical Chemistry for Technicians, Lewis Publishers, Inc., Michigan, 1989 Lodge, J.P., Methods of Air Sampling and Analysis, 3rd edition, Lewis Publi. Inc., Michigan, 1991

15

25.

LaQue, F.L. and Copson, H.R., Corrosion Resistance of Metals and Alloys, 2nd Ed., American Chemical Society Monograph No. 158, New York, 1963

16

Appendix 1: HCFC Blend A Concentrations Measured by GC/MS HAPE 2-13 March-April 1995

SAMPLE TIME of F22 F124 F123 AGENT Sampling % % % as sum % min HAPE 2, 17-Feb-95 8.6%NAFS III T2-1 0.5 0.00 0.00 0.00 0.00 T2-2 2 2.48 0.18 0.23 2.88 T2-3 3.5 2.36 0.18 0.24 2.79 T2-5 6.5 2.04 0.20 0.29 2.52 T2-6 8 3.10 0.21 0.31 3.62 T2-7 9.5 2.82 0.21 0.30 3.33 T2-8 11 2.34 0.19 0.28 2.82 T2-10 15.5 2.70 0.18 0.26 3.13 T2-11 18.5 2.04 0.15 0.23 2.42 T2-12 21.5 1.33 0.11 0.18 1.63 HAPE 3, 22-Feb-95 8.6%NAFS III T3-1 0.5 0.00 T3-2 1 2.44 T3-3 2 2.91 T3-5 5 2.63 T3-6 6.5 2.09 T3-8 12.5 2.19 T3-9 14 1.02 T3-10 17 0.58 T3-11 23 0.00 HAPE 4, 24-Feb-95 9.3%NAFS III T4-1 0 0.00 T4-2 0.5 0.26 T4-3 1 2.91 T4-4 2 2.22 T4-5 3.5 2.80 T4-6 5 2.90 T4-8 8 2.77 T4-9 9.5 2.14 T4-10 11 2.21 T4-11 14 1.20 T4-12 20 0.63 HAPE 5, 28-Feb-95 9.3%NAFS III T5-1 0 0.00 T5-2 0.5 0.06 T5-3 1 3.79 T5-4 2 2.18 T5-5 3.5 3.84 T5-6 5 4.79 T5-7 8 3.06 T5-8 11 4.03

0.00 0.16 0.18 0.16 0.15 0.14 0.11 0.08 0.06

0.00 0.24 0.24 0.23 0.22 0.21 0.16 0.12 0.08

0.00 2.85 3.33 3.02 2.45 2.54 1.29 0.79 0.13

0.05 0.05 0.15 0.12 0.14 0.14 0.13 0.11 0.11 0.08 0.05

0.00 0.00 0.21 0.18 0.19 0.18 0.20 0.18 0.16 0.13 0.00

0.05 0.31 3.27 2.52 3.13 3.23 3.09 2.43 2.49 1.41 0.69

0.00 0.00 0.36 0.19 0.27 0.32 0.30 0.29

0.00 0.02 0.24 0.17 0.19 0.20 0.19 0.20

0.00 0.08 4.39 2.54 4.30 5.31 3.56 4.52

17

T5-9 T5-11

12.5 20.5

2.28 0.43

0.17 0.01

0.12 0.00

2.57 0.44

HAPE 6, 02-Mar-95 9.3%NAFS III T6-1 0 -0.00 T6-2 0.5 -0.00 T6-3 1 0.49 T6-4 2 1.04 T6-5 3.5 1.77 T6-6 5 1.69 T6-7 6.5 1.34 T6-8 9.5 1.38 T6-9 12.5 0.79 T6-10 15.5 0.59 T6-11 20.5 0.34 HAPE 7, 07-Mar-95 9.3%NAFS III T7-1 0 -0.00 T7-2 0.5 -0.00 T7-3 1 3.40 T7-4 2 4.72 T7-5 3.5 3.68 T7-6 5 4.52 T7-7 6.5 4.29 T7-8 9.5 7.52 T7-9 12.5 3.92 T7-10 18.5 1.79 T7-11 24 0.40 HAPE 8, 09-Mar-95 9.3%NAFS III T8-1 0 T8-2 0.5 T8-3 1 T8-4 2 3.75 T8-5 3.5 3.48 T8-6 5 2.43 T8-7 6.5 2.80 T8-8 9.5 5.23 T8-9 12.5 2.39 T8-10 17 1.84 HAPE 9, 16-Mar-95 8.6%NAFS III T9-1 0 -0.00 T9-2 0.5 -0.00 T9-3 1 0.28 T9-4 2 5.37 T9-5 3.5 4.60 T9-6 5 3.07 T9-7 8 5.03 T9-8 11 5.76 T9-9 12.5 8.46 T9-10 15.5 1.53

0.00 0.00 0.06 0.05 0.09 0.08 0.10 0.08 0.07 0.03 0.02

0.00 0.00 0.06 0.04 0.08 0.06 0.08 0.06 0.05 0.02 0.00

-0.00 -0.00 0.61 1.13 1.94 1.83 1.53 1.52 0.91 0.65 0.36

0.00 0.00 0.24 0.47 0.40 0.43 0.43 0.56 0.34 0.08 0.02

0.00 0.03 0.18 0.41 0.34 0.31 0.32 0.38 0.24 0.08 0.03

-0.00 0.03 3.82 5.59 4.42 5.26 5.04 8.46 4.50 1.96 0.45

n/d n/d n/d 0.34 0.35 0.36 0.38 0.45 0.20 0.11 0.30 0.29 0.28 0.28 0.30 0.15 0.08 4.39 4.11 3.06 3.46 5.98 2.74 2.03

0.00 0.00 0.02 0.45 0.44 0.43 0.49 0.49 0.50 0.12

0.01 0.01 0.03 0.33 0.32 0.34 0.37 0.42 0.37 0.10

0.01 0.01 0.32 6.15 5.36 3.84 5.88 6.68 9.34 1.76

HAPE 10, 21-Mar-95 2x8.6%NAFS III T10-1 0 -0.00 0.00 T10-2 0.5 -0.00 0.00

0.00 0.00

-0.00 -0.00

18

T10-3 T10-4 T10-5 T10-6 T10-7 T10-8 T10-9 T10-10 T10-11 T10-12

1 2 3.5 5 6.5 9.5 11 12.5 17 27.5

-0.00 4.48 5.90 12.66 8.45 12.79 4.78 3.54 2.27 0.14 8.6%NAFS III -0.00 5.40 4.78 4.74 4.67 6.01 5.06 4.64 1.22

0.18 0.55 0.61 1.09 0.85 0.97 0.45 0.36 0.19 0.00

0.11 0.52 0.59 0.69 0.65 0.58 0.31 0.28 0.15 0.00

0.29 5.54 7.10 14.44 9.95 14.34 5.54 4.18 2.61 0.14

HAPE 11, 22-Mar-95 T11-1 0 T11-2 0.5 T11-3 1 T11-4 2.5 T11-6 5.5 T11-7 7 T11-8 8.5 T11-9 11.5 T11-10 13 T11-11 17.5 HAPE 13, T13-1 T13-2 T13-3 T13-4 T13-5 T13-6 T13-7 24-Mar-95 0 0.5 1 2.5 4 5.3 8.5

0.00 0.39 0.38 0.38 0.38 0.44 0.43 0.28 0.05

0.00 0.29 0.29 0.29 0.33 0.35 0.36 0.25 0.08

-0.00 6.09 5.45 5.41 5.38 6.80 5.85 5.17 1.35

10%NAFS III -0.00 0.00 -0.00 0.00 4.38 0.27 5.32 0.46 4.11 0.34 4.58 0.37 6.65 0.40

0.00 0.00 0.22 0.34 0.27 0.29 0.33

-0.00 -0.00 4.86 6.13 4.73 5.24 7.39

19

Appendix 2: F- and Cl- Concentration Measured by Ion Selective Electrode Method HAPE 3 - 13 March - April 1995 Sample middle time s Cl- conc in gas ppm F- conc in gas ppm

HAPE 3, 22-Feb-95 3-01 3-02 3-03 3-04 3-07 3-08 HAPE 4, 24-Feb-95 4-01 4-02 4-03 4-04 4-05 4-07 HAPE 5, 28-Feb-95 5-01 5-02 5-04 5-05 5-06 5-09 5-10 5-11 HAPE 6, 02-Mar-95 6-01 6-02 6-03 6-04 6-05 6-06 6-07 6-08 6-09 HAPE 7, 07-Mar-95 7-01 7-02

8.6%NAFS III 0 30 95.5 172 242 525 705 9.3%NAFS III 0 120 285 375 465 573 1140 9.3%NAFS III 0 60 150 270 330 390 705 855 1095 9.3%NAFS III 0 60 180 300 420 540 660 900 1140 9.3%NAFS III 0 60

0 28 2598 1852 3887 16765 14501

0 26 5978 8425 12429 13250 10955

0 2633 19383 23519 21351 20343 4780

0 3397 11821 11379 12279 12755 5834

0 3942 5619 11058 12181 14781 14508 8310 4882

0 7409 12727 13220 13733 13733 10660 4398 4076

14 1817 4555 9407 11980 14537 11980 8540 3754

116 5616 9566 9209 8535 8535 7909 4824 2527

15 1394

47 3475

20

7-03 7-04 7-05 7-06 7-07 7-08 HAPE 8, 09-Mar-95

180 300 420 540 840 1140 9.3%NAFS III 0 55 235 303 415 535 655 900 1140 8.6%NAFS III 0 55 175 295 415 535 660 900 1140

1955 5398 9189 11149 9644 3022

6635 8025 7160 6635 5281 2202

8-01 8-02 8-03 8-04 8-05 8-06 8-07 8-08 HAPE 9, 16-Mar-95

0 1058 1615 5516 4513 6032 4300 1732 387

0 4076 4857 9155 7211 7491 6683 2863 1065

9-01 9-02 9-03 9-04 9-05 9-06 9-07 9-08

0 1307 1511 1665 2225 2120 2141 897 255

0 4295 8517 8199 8517 7599 6966 2591 1258

HAPE 10, 21-Mar-95 2x8.6%NAFS III 0 55 175 297 474 535 660 895 1014 1140 0 1983 2184 2436 2572 2406 627 465 337 170 0 4351 4695 5479 5360 4877 2625 2279 1528

10-01 10-02 10-03 10-04 10-05 10-06 10-07 10-08 10-09

HAPE 11, 22-Mar-95

8.6%NAFS III 0 55 175 295 415 535 670 797.5 0 1457 1684 1388 1855 1388 1769 944 0 3483 3904 5710 8354 7175 6319 4189

11-01 11-02 11-03 11-04 11-05 11-06 11-07

21

11-08 11-09 HAPE 13, 24-Mar-95

895 1020 10%NAFS III

610 345

2879 1737

13-01 13-02 13-04 13-05 13-06 13-07 13-08 13-09

0 65 182.5 415 535 655 782.5 912 1095

0 1218 2229 2834 3438 2974 1614 854 422

0 3242 8470 8848 8848 7042 3779 2311 1538

22

Table 1
Test Date 1995 Jan-27 Feb-17 Feb-22

Sequence of Tests in Phase 1 of HAPE Project

Target Conc. HCFC Blend A (%) 8.6 8.6 8.6 Pipe System Nozzle/ Orifice Diam. Type A 8.8 mm Type A 11.5 mm Type A 11.5 mm Type A 11.5 mm Type A 11.5 mm Type B 6 @ 8 mm Type B 6 @ 8 mm Type B 6 @ 8 mm Type B 6 @ 8 mm Fire Comments Details

H-1 H-2 H-3

Navy standard 65 mm manifold Navy standard 65 mm manifold Navy standard 65 mm manifold Navy standard 65 mm manifold Navy standard 65 mm manifold Navy standard 65 mm manifold Navy standard 65 mm manifold Modified Removed 65 mm manifold Modified Removed 65 mm manifold Replaced 65 mm manifold two cylinders discharge Navy standard 65 mm manifold

None 8 TTs (see Note) 8 TTs 3 SPs 200 kW 8 TTs 1 RPs 450 kW 8 TTs 3 SPs 200 kW 8 TTs 3 SPs 200 kW 8 TTs 3 SPs 200 kW 8 TTs 3 SPs 200 kW 8 TTs 2 SPs 1 RP in centre 550 kW 8 TTs 3 SPs 200 kW

H-4

Feb-24

8.6

SPs 50 mm from each wall RP between nozzles SPs 50 mm from each wall Gas sampling lines adjusted vertically SPs 50 mm from each wall SPs 50 mm from each wall 1 SP moved out to 300 mm from each wall SPs 50 mm from each wall

H-5

Feb-28

9.3

H-6

Mar-2

9.3

H-7

Mar-7

9.3

H-8

Mar-9

9.3

H-9

Mar-16

9.3

H-10

Mar-21

3 SPs SPs 50 mm 150 kW from each Pans in wall corners H-12 Mar-23 No discharge N/A N/A 3 SPs Non150 kW suppression Pans in test corners H-13 Mar-24 10 Navy standard Type B 8 TTs SPs 50 mm 65 mm manifold 6 @ 8 mm 3 SPs from each 200 kW wall Note: Total heat output from eight TTs is estimated to be 50 kW; three SPs, 150 kW; one RP, 400 kW

H-11

Mar-22

2 @ 8.6 Target 15 with controlled venting 8.6 Post-discharge ignition

Type B 6 @ 8 mm

Type B 6 @ 8 mm

23

12 H-2 H-3 H-7 H-8

10

Volumetric Concentration (%)

0 60 90 120 Time (s) 150 180

Figure 3a. HCFC Blend A concentration-time profiles measured by FTIR Spectroscopy for Tests H-2, H-3, H-7 and H-8.

24

16

14

12 Volumetric Concentration (%)

10

8 H-9 H-10 H-11 H-13

0 60 90 120 Time (s) 150 180

Figure 3b. HCFC Blend A concentration-time profiles measured by FTIR Spectroscopy for Tests H-9, H-10, H-11 and H-13.

25

12

10

H-2 H-3 H-7 H-8

Volumetric Concentration (%)

0 0 200 400 600 Time (S) 800 1000 1200 1400

Figure 4a. HCFC Blend A concentration-time profiles measured by GC/MS for Tests H-2, H-3, H-7 and H-8.

26

16 H-9 H-10 H-11 H-13

14

12 Volumetric Concentration (%)

10

0 0 200 400 600 Time (S) 800 1000 1200 1400

Figure 4b. HCFC Blend A concentration-time profiles measured by GC/MS for Tests H-9, H-10, H-11 and H-13.

27

18000 16000 14000 Volumetric Concentration (ppm) 12000 10000 8000 6000 4000 2000 0 0 60 120 180 240 300 360 420 480 540 600 660 720 780 840 900 960 Time (s) H-2 (FTIR) H-3 (FTIR) H-3 (SIE)

Figure 5a. HF concentration-time profiles measured by FTIR and SIE for Tests H-2 and H-3.

28

18000 16000 14000 Volumetric Concentration (ppm) 12000 10000 8000 6000 4000 2000 0 0 60 120 180 240 300 360 420 480 540 600 660 720 780 840 900 960 Time (s) H-2 (FTIR) H-3 (FTIR) H-3 (SIE)

Figure 5b. HCI concentration-time profiles measured by FTIR and SIE for Tests H-2 and H-3.

29

40000 H-8 (FTIR) H-9 (FTIR) H-13 (FTIR) H-8 (SIE) H-9 (SIE) H-13 (SIE)

35000

Volumetric Concentration (ppm)

30000

25000

20000

15000

10000

5000

0 60 120 180 240 300 360 420 480 540 600 660 720 Time (s)

Figure 6a. HF concentration-time profiles measured by FTIR and SIE for Tests H-8, H-9 and H-13.

30

25000 H-8 (FTIR) H-9 (FTIR) H-13 (FTIR) H-8 (SIE) H-9 (SIE) H-13 (SIE)

20000 Volumetric Concentration (ppm)

15000

10000

5000

0 60 120 180 240 300 360 420 480 540 600 660 720 Time (s)

Figure 6b. HCI concentration-time profiles measured by FTIR and SIE for Tests H-8, H-9 and H-13.

31

6000

5000 HF and HCI Concentration (ppm) HF (FTIR) HCl (FTIR) HF (SIE) HCI (SIE)

4000

3000

2000

1000

0 60 120 180 240 300 360 420 480 540 600 660 720 Time (s)

Figure 7. HF and HCI concentration-time profiles measured by FTIR and SIE for Test H-10.

32

6 HCFC-22 HCFC-124 HCFC-123

Volumetric Concentration (%)

0 0 200 400 600 Time (s) 800 1000 1200

Figure 8. The components of HCFC Blend A-time profiles measured by GC/MS for Tests H-8.

33