NIRS法测定甲醛溶液中甲醛含量的方法研究
魏钠,陈安梅,马伟,王明,朱凤萍,周洪涧,张琳
(万华化学(宁波)有限公司,浙江,宁波,315812)
Determination of formaldehyde content informaldehyde solution by Near Infrared Spectrometer
WEI Na, CHEN An-mei, MA Wei, WANG Ming, ZHU Feng-ping, ZHOU Hong-jian
ZHANG Ling
(WAN HUA Chemical (Ningbo) Co., Ltd., Zhejiang, Ningbo,315812,China)
图1 近红外光谱图
Fig1 NIRS transmission spectra
图2 近红外模型曲线光谱图
Fig2NIRS transmission spectra
3.3 测量系统的稳定性试验Table1 Result by MSA
量具研究 | |||||||||
量具(近红外光谱仪) | 分析员 | ||||||||
样品名称 | A | A | A | B | B | B | C | C | C |
样品1 | 36.9 | 36.9 | 37.0 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 |
样品2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 |
样品3 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 |
样品4 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 |
样品5 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.7 | 36.8 | 36.8 | 36.8 |
样品6 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 | 36.8 |
样品7 | 36.7 | 36.7 | 36.7 | 36.7 | 36.7 | 36.7 | 36.7 | 36.7 | 36.7 |
样品8 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 |
样品9 | 37.0 | 37.0 | 37.0 | 37.0 | 37.0 | 36.9 | 37.0 | 37.0 | 37.0 |
样品10 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 | 36.9 |
样品11 | 37.3 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.2 | 37.1 | 37.2 |
表2 NIRS法测量结果
Table2 Measuredresult by NIRSmethod
样品名称 | 近红外测值 | 电位滴定法 | 极差 |
样品1 | 37.41 | 37.4 | 0.01 |
样品2 | 36.76 | 36.8 | -0.04 |
样品3 | 35.17 | 35.2 | -0.03 |
样品4 | 36.79 | 36.7 | 0.09 |
样品5 | 22.65 | 22.7 | -0.05 |
样品6 | 21.71 | 21.7 | 0.01 |
样品7 | 37.3 | 37.1 | 0.2 |
样品8 | 37.1 | 37.2 | -0.1 |
样品9 | 28.85 | 28.7 | 0.15 |
样品10 | 31.77 | 31.7 | 0.07 |
样品11 | 46.81 | 46.7 | 0.11 |
样品12 | 45.1 | 45.1 | 0 |
样品13 | 22.88 | 22.9 | -0.02 |
样品14 | 36.66 | 36.5 | 0.16 |
样品15 | 21.65 | 21.7 | -0.05 |
样品16 | 37.13 | 37.1 | 0.03 |
样品17 | 47.09 | 47.2 | -0.11 |
样品18 | 45.04 | 45 | 0.04 |
样品19 | 37.37 | 37.5 | -0.13 |
样品20 | 36.93 | 37.1 | -0.17 |
样品21 | 34.42 | 34.4 | 0.02 |
样品22 | 36.47 | 36.6 | -0.13 |
样品23 | 36.94 | 37 | -0.06 |
样品24 | 37.22 | 37.2 | 0.02 |
样品25 | 37.37 | 37.3 | 0.07 |
样品26 | 37.32 | 37.4 | -0.08 |
样品27 | 36.53 | 36.8 | -0.27 |
样品28 | 37.05 | 36.8 | 0.25 |
样品29 | 37.08 | 37.1 | -0.02 |
样品30 | 37.1 | 37.2 | -0.1 |
样品31 | 37.21 | 37.3 | -0.09 |
样品32 | 37.22 | 37.1 | 0.12 |
样品33 | 37.2 | 37.1 | 0.1 |
样品34 | 37.12 | 37.25 | -0.13 |
样品35 | 37 | 36.9 | 0.1 |
样品36 | 37.21 | 37 | 0.21 |
样品37 | 37.42 | 37.4 | 0.02 |
样品38 | 37.68 | 37.5 | 0.18 |
样品39 | 36.66 | 36.5 | 0.16 |
样品40 | 37.35 | 37.4 | -0.05 |
样品41 | 37.37 | 37.2 | 0.17 |
样品42 | 37.23 | 37.4 | -0.17 |
样品43 | 37.03 | 37.2 | -0.17 |
样品44 | 37.56 | 37.3 | 0.26 |
样品45 | 37.29 | 37.4 | -0.11 |
样品46 | 37.29 | 37.4 | -0.11 |
样品47 | 37.23 | 37.2 | 0.03 |
样品48 | 37.43 | 37.3 | 0.13 |
样品49 | 37.29 | 37.4 | -0.11 |
样品50 | 37.62 | 37.5 | 0.12 |
样品51 | 37.45 | 37.5 | -0.05 |
样品52 | 37.53 | 37.5 | 0.03 |
样品53 | 36.82 | 36.8 | 0.02 |
样品54 | 37.41 | 37.3 | 0.11 |
样品55 | 37.3 | 37.1 | 0.2 |
样品57 | 37.35 | 37.2 | 0.15 |
样品58 | 37 | 37.1 | -0.1 |
样品59 | 37.29 | 37.1 | 0.19 |
样品60 | 37.06 | 36.8 | 0.26 |
样品61 | 37.01 | 37 | 0.01 |
样品62 | 36.72 | 36.9 | -0.18 |
样品63 | 37.4 | 37.2 | 0.2 |
样品64 | 36.96 | 36.8 | 0.16 |
样品65 | 37.53 | 37.7 | -0.17 |
样品66 | 36.63 | 36.7 | -0.07 |
样品67 | 36.89 | 36.9 | -0.01 |
样品68 | 37.36 | 37.3 | 0.06 |
样品69 | 37.13 | 37.2 | -0.07 |
样品72 | 37.31 | 37.2 | 0.11 |
样品73 | 37 | 36.86 | 0.14 |
样品74 | 36.85 | 36.76 | 0.09 |
样品75 | 37.28 | 37.4 | -0.12 |
样品76 | 37.26 | 37.2 | 0.06 |
样品77 | 37.07 | 37.09 | -0.02 |
样品78 | 37.18 | 37.3 | -0.12 |
样品79 | 37.58 | 37.4 | 0.18 |
样品80 | 36.88 | 37.0 | -0.12 |
表3 MSA分析数据结果
Table3 Result by MSA
方差分量 | 方差分量贡献率 | 标准差(SD) | 研究变异 (6*SD) | %研究变异(%SV) | |
合计量具R&R | 0.0001521 | 0.62 | 0.012333 | 0.074001 | 7.87 |
重复性 | 0.0001153 | 0.47 | 0.010739 | 0.064436 | 6.85 |
再现性 | 0.0000368 | 0.15 | 0.006065 | 0.036387 | 3.87 |
部件间 | 0.0244307 | 99.38 | 0.156303 | 0.937819 | 99.69 |
合计变异 | 0.0245828 | 100.00 | 0.156789 | 0.940734 | 100.00 |
可区分的类别数=17 |
图3 近红外法和国标法之间的极差正态检验
Fig3 Range normal test of the difference between NIRSand NS
双样本T检验和置信区间 | |||
均值 | 标准差 | 均值标准误差 | |
近红外测定甲醛 | 36.82 | 3.78 | 0.27 |
企标法测定甲醛 | 36.82 | 3.79 | 0.27 |
差值=mu(近红外测值)-(企标法测值) | |||
差值估计值:-0.005 | |||
平均差的95%置信区间 | (-0.752,0.743) | ||
平均差=0(与≠)的T检验:T值=-0.01 P值=0.990 | |||
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参考文献.