Stability Assessment of Gas Mixtures Containing Monoterpenes in Varying Cylinder Materials and Treatments Jerry Rhoderick and Janice Lin Analytical Chemistry Division National Institute of Standards and Technology 100 Bureau Drive, MS-8393 Gaithersburg, Maryland 20899-8393 USA 4th WMO-VOC meeting on Global Observations of VOCs September 12, 2012 York, United Kingdom
Ratios of terpenes to benzene with time in mixture ND02744 Aluminum Aculife Cylinder
Tracking the growth/degradation rates for ß-pinene, α-pinene, R-limonene, p-cymene and camphene in mixture ND02744
Publications on ß-Pinene and α-pinene Isomerization Foletto E, Valentini A, Probst L, Porto L., 2002. Gas-phase ß-pinene isomerization over acid-activated bentonite. Latin American Applied Research 32(2). Allahverdiev A, Gündüz G, Murzin D., 1998. Kinetics of α-pinene isomerization. Industrial Engenering and Chemical Research 37, 2373-2377. Findik S, Gündüz G., 1997. Isomerization of α-pinene to camphene. JAOCS 74(9), 1145-1151.
Concentration of Standards Prepared Experis Treated Aluminum Nickel-Plated Carbon Steel D646508 D646507 41311187Y 41311192Y 41311193Y Analyte x a u(x) b x a u(x) b x a u(x) b x a u(x) b x a u(x) b α-pinene 12.88 0.13 0.021 0.002 1.41 0.05 0.010 0.001 0.006 0.001 ß-Pinene 9.91 0.17 5.34 0.22 4.65 0.18 2.57 0.23 3-Carene 0.009 0.004 9.56 0.13 4.10 0.27 9.07 0.26 3.33 0.13 1,8-Cineole 0.015 0.001 0.014 0.002 4.48 0.21 6.63 0.19 2.31 0.28 Myrcene 1.92 0.19 R-Limonene 9.32 0.13 0.003 0.0002 0.002 0.0002 0.001 0.0002 p-cymene 0.008 0.002 10.70 0.16 0.026 0.001 0.041 0.002 0.015 0.001 Camphene 0.001 0.001 9.58 0.25 0.004 0.001 0.005 0.001 0.002 0.001 n-hexane 14.19 0.30 11.51 0.29 8.82 0.28 4.60 0.26 Benzene 14.74 0.30
RATIO Data and Statistics for Ni plated steel 41311192Y 3-Carene 1,8-Cineole β-pinene α-pinene p-cymene Camphene R- Limonene Days DateTime Ratio U(Rat) Ratio U(Rat) Ratio U(Rat) Ratio U(Rat) Ratio U(Rat) Ratio U(Rat) Ratio U(Rat) 1 23-Mar-12 1.5503 0.0123 1.3061 0.0131 0.8334 0.0082 0.0736 0.0006 0.0288 0.0009 0.0111 0.0021 0.0133 0.0006 6 28-Mar-12 1.5462 0.0202 1.3038 0.0275 0.8324 0.0111 0.0746 0.0011 0.0281 0.0014 0.0166 0.0019 0.0110 0.0011 7 29-Mar-12 1.5551 0.0360 1.2945 0.0350 0.8300 0.0058 0.0745 0.0009 0.0281 0.0006 0.0185 0.0009 0.0110 0.0004 14 5-Apr-12 1.5271 0.0079 1.3049 0.0086 0.8203 0.0048 0.0753 0.0009 0.0281 0.0007 0.0160 0.0014 0.0116 0.0009 19 10-Apr-12 1.5194 0.0058 1.3028 0.0051 0.8164 0.0033 0.0755 0.0010 0.0283 0.0012 0.0191 0.0018 0.0117 0.0007 20 11-Apr-12 1.5186 0.0130 1.3040 0.0106 0.8157 0.0067 0.0751 0.0008 0.0281 0.0004 0.0190 0.0007 0.0121 0.0006 22 13-Apr-12 1.5139 0.0143 1.2967 0.0116 0.8131 0.0074 0.0751 0.0009 0.0284 0.0006 0.0181 0.0008 0.0120 0.0003 29 20-Apr-12 1.5053 0.0090 1.2929 0.0081 0.8109 0.0042 0.0756 0.0017 0.0269 0.0002 0.0167 0.0021 0.0119 0.0003 33 24-Apr-12 1.5168 0.0067 1.2982 0.0075 0.8155 0.0036 0.0761 0.0013 0.0273 0.0002 0.0189 0.0006 0.0118 0.0005 35 26-Apr-12 1.5082 0.0100 1.2907 0.0093 0.8116 0.0054 0.0760 0.0015 0.0267 0.0003 0.0165 0.0002 0.0111 0.0005 36 27-Apr-12 1.5176 0.0260 1.2787 0.0158 0.8120 0.0047 0.0759 0.0010 0.0264 0.0004 0.0165 0.0003 0.0117 0.0012 56 17-May-12 1.4837 0.0029 1.2765 0.0042 0.7994 0.0006 0.0801 0.0024 0.0260 0.0008 0.0155 0.0006 0.0115 0.0005 61 22-May-12 1.4823 0.0032 1.2691 0.0067 0.7977 0.0020 0.0793 0.0013 0.0260 0.0002 0.0146 0.0020 0.0113 0.0012 62 23-May-12 1.4825 0.0128 1.2742 0.0110 0.7972 0.0063 0.0802 0.0015 0.0257 0.0012 0.0154 0.0006 0.0113 0.0006 69 30-May-12 1.4753 0.0066 1.2693 0.0077 0.7924 0.0031 0.0812 0.0022 0.0258 0.0001 0.0156 0.0010 0.0117 0.0005 81 11-Jun-12 1.4681 0.0058 1.2663 0.0067 0.7888 0.0035 0.0816 0.0005 0.0253 0.0005 0.0172 0.0005 0.0114 0.0008 n 16 16 16 16 16 16 16 Average 1.5107 0.0148 1.2893 0.0142 0.8117 0.0056 0.0769 0.0013 0.0271 0.0007 0.0166 0.0013 0.0116 0.0007 Stdev 0.0268 0.0145 0.0137 0.0026 0.0012 0.0020 0.0005 %RSD 1.77% 1.12% 1.69% 3.44% 4.27% 12.24% 4.68% Slp; Intr -0.00105 1.5467-0.00055 1.3083-0.00054 0.8304 0.00010 0.0733-0.000045 0.0287-0.00001 0.0168-0.00001 0.0119 u(slp); u(intr) 0.00008 0.0034 0.00006 0.0023 0.00003 0.0014 0.00001 0.0003 0.000004 0.0002 0.00002 0.0009 0.00001 0.0002 R 2 ; RMSE 0.924 0.008 0.874 0.005 0.948 0.003 0.937 0.001 0.903 0.0004 0.008 0.002 0.103 0.001 slp /u(slp) 13.08 9.88 15.95 14.47 11.41 0.34 1.26 p 0.00 0.00 0.00 0.00 0.00 0.74 0.23
Minor Component Peak Area Ratios Major Component Peak Area Ratios Major Monoterpene and Minor (Impurity) Analyte Ratios in CSNi-92Y 1.60 1.40 1.20 1.00 3-Carene 1,8-Cineole ß-Pinene α-pinene p-cymene Camphene R-Limonene Initial Linear Trend 0.80 0.60 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 10 20 30 40 50 60 70 80 90 Time, Days from Preparation
Minor Component Peak Area Ratios Major Component Peak Area Ratios Major Monoterpene and Minor (Impurity) Analyte Ratios in CSNi-87Y 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.008 ß-Pinene 1,8-Cineole 3-Carene α-pinene Camphene p-cymene R-Limonene Initial Linear Trend 0.006 0.004 0.002 0.000 0 10 20 30 40 50 Time, Days from Preparation
Minor Component Peak Area Ratios Major Component Peak Area Ratios Major Monoterpene and Minor (Impurity) Analyte Ratios in CSNi-93Y 0.95 0.85 0.75 0.65 0.55 0.45 0.35 0.024 0.020 ß-Pinene 3-Carene 1,8-Cineole α-pinene Camphene p-cymene R-Limonene Initial Linear Trend 0.016 0.012 0.008 0.004 0.000 5 10 15 20 25 30 35 40 Time, Days from Preparation
Major Monoterpene and Minor (Impurity) Analyte Ratios in Al-Experis D646508
Ratios Ratios Major Monoterpene and Minor (Impurity) Analyte Ratios in Al-Experis Camphene β-pinene D646507 p-cymene R-Limonene 3-Carene 1.6 Initial Linear Trend Myrcene α-pinene 1.4 1.2 1.0 0.8 0.6 0.12 0.1 0.08 0.06 0.04 0.02 0 50 100 150 200 250 300 0 0 n 17 50 17 100 17 150 17 200 17 250 17 17 300 Average 1.4508 0.0222 1.2496 0.0167 1.0641 0.0159 0.9389 0.0141 0.7188 0.0110 0.1291 0.0027 0.0100 0.0003 Stdev 0.0095 0.0025 0.0033 0.0033 0.0030 0.0026 0.0016 %RSD 0.65% 0.20% 0.31% 0.36% 0.41% 2.02% 15.96% Camphene ß-Pinene p-cymene R-Limonene 3-Carene Myrcene α-pinene Slp Intr -0.000001 1.4510 0.000016 1.2476-0.00001 1.0653-0.000002 0.9391-0.00002 0.7208 0.000020 0.1267-0.000013 0.0116 u(slp) u(intr) 0.000025 0.0039 0.000005 0.0008 0.000008 0.0013 0.000009 0.0014 0.000006 0.0010 0.000005 0.0007 0.000002 0.0004 R RMSE 0.000 0.010 0.413 0.002 0.090 0.003 0.004 0.003 0.306 0.003 0.554 0.002 0.704 0.001 slp /u(slp) 0.06 3.25 1.21 0.24 2.57 4.31 5.97 Prob 0.95 0.01 0.24 0.81 0.02 0.00 0.00 Days
Ratios for ß-pinene in CSNi-92Y, CSNi-87Y, CSNi-93Y, Al-Experis-07, and Al-Aculife Cylinders.
Gravimetric Concentration of Additional Standards Prepared Aluminum Experis Treated Experis Treated Aluminum D646508 (20L) D750499 (10L) Analyte x a u(x) b x a u(x) b α-pinene 6.04 0.09 7.58 0.14 ß-Pinene 4.82 0.06 3.76 0.23 3-Carene 2.99 0.06 5.72 0.14 1,8-Cineole 4.74 0.006 4.96 0.09 R-Limonene 0.002 0.001 2.25 0.07 p-cymene 0.025 0.002 0.031 0.02 Camphene 0.004 0.001 0.003 0.001 n-hexane 9.65 0.11 2.34 0.25
Major Monoterpene Analyte Ratios in Remake Al-Experis D646508 n 12 12 12 12 Average 1.1616 0.0109 0.8751 0.0081 0.7877 0.0076 0.4677 0.0043 Stdev 0.0041 0.0033 0.0031 0.0016 %RSD 0.35% 0.38% 0.39% 0.35% α-pinene ß-Pinene 1,8-Cineole 3-Carene Slp Intr 0.000140 1.1574 0.00012335 0.8714 0.0001191 0.7841 0.000058 0.4659 u(slp) u(intr) 0.000040 0.0015 0.000028 0.0010 0.000025 0.0009 0.000015 0.0005 R RMSE 0.552 0.003 0.658 0.002 0.700 0.002 0.605 0.001 slp /u(slp) 3.51 4.39 4.83 3.92 Prob 0.01 0.00 0.00 0.00
Bi-lateral comparison with NIST
Values of NPL Standard vs NIST Standards
Results from Round Robin of ppt Hydrocarbon Mixture
Where do we go from here? develop several standards at higher concentration - 100-200 nmol/mol - verify concentrations prepare several 2-5 nmol/mol standards by dilution from higher concentration - verify gravimetric concentrations - compare to older 1-step standards - this procedure will lower the uncertainties substantially
Conclusions Air Products aluminum w/experis treatment very promising - nickel plate steel cylinders show degradation but a much slower rate than Aculifed aluminum results indicate stable (365+ days) mixtures of α-pinene, ß-pinene, 3-carene, p-cymene, R-limonene, camphene -1,8-cineole at 70+ days