粗精硝基苯纯度及杂质分析方法整合探究
崔华宝 叶冬芸 邓颖良
(万华化学(宁波)有限公司,浙江省 宁波市 315812)
由于粗硝基苯和精硝基苯在苯组分含量上相差6%,且苯和其它各组分响应差异较大,所以面积百分比法并不能完全适用于二者纯度及杂质的分析。
图1 粗硝基苯校正表
图2精硝基苯化合物表
图3 粗硝基各组分色谱图
图4精硝基各组分色谱图
1、线性方程
如下直线方程属于·线性方程:
y=kx+b
图像可表示为:
图5 线性方程图
2、线性拟合
线性拟合是曲线拟合的一种形式,通过一组观测数据来寻求最佳的理论曲线,使得观测数据与理论曲线之间的误差最小。在实际应用中,具体来说,线性拟合是通过找到一条最佳拟合直线,这条直线能够最好地匹配给定的数据点。
如下图所示:
图6 拟合线图
线性拟合就是根据一组x, y的值,来寻求最佳k,b的值,这个过程也可称为线性回归。
此方法利用安捷伦气相色谱技术,使用一根HP-5色谱柱让组分进行分离,粗精硝基苯纯度及杂质,分别通过FID检测器进行归一化和面积百分比法定量。将归一化和面积百分比法组分含量之间的关系,进行线性模型的拟合,利用拟合方程,预测面积百分比法组分含量所对应的归一化法组分含量。
本方案实现了粗精硝基苯纯度及杂质,分析方法整合运用;降低了人员和有毒有害试剂的使用,可以快速搭建分析方法,出具分析数据,提高了工作效率。对硝苯装置的生产具有重要的指导意义。
利用CDS操作系统,随机选取2024年5-8月份粗硝基苯样品序列,分别使用归一化和面积百分比法,测定各组分含量,录入表单,制成基础数据表。
色谱图如下:
图7 各组分归一化和面积百分比法含量色谱图
表1苯基础数据:
数量 | 样品 | 归一化苯% | 面积百分比苯% |
1 | 2211B 24-5-4 | 6.4960 | 10.1291 |
2 | 2221B 24-5-4 | 6.5511 | 10.2134 |
3 | 2211B 24-5-7 | 6.3141 | 9.8420 |
4 | 2221B 24-5-7 | 6.5609 | 10.2281 |
5 | 2211B 24-5-7 | 6.3133 | 9.857 |
6 | 2211B 24-5-9 | 6.4160 | 9.9991 |
7 | 2211B 24-5-11 | 6.6318 | 10.308 |
8 | 2221B 24-5-11 | 6.7084 | 10.4229 |
9 | 2211B 24-5-14 | 6.5440 | 10.1838 |
10 | 2221B 24-5-14 | 6.2823 | 9.7961 |
11 | 2211B 24-5-16 | 6.3177 | 9.8382 |
12 | 2221B 24-5-16 | 6.3221 | 9.8468 |
13 | 2211B 24-5-18 | 6.2255 | 9.6862 |
14 | 2221B 24-5-18 | 6.3405 | 9.8612 |
15 | 2211B 24-5-21 | 6.4130 | 9.9781 |
16 | 2221B 24-5-21 | 6.5037 | 10.1172 |
17 | 2211B 24-5-23 | 6.8949 | 10.7144 |
18 | 2221B 24-5-23 | 6.7634 | 10.5216 |
19 | 2211B 24-5-25 | 6.9460 | 10.7991 |
20 | 2221B 24-5-25 | 6.8651 | 10.68 |
21 | 2211B 24-5-28 | 7.0561 | 10.9576 |
22 | 2221B 24-5-28 | 6.8674 | 10.6797 |
23 | 2211B 24-5-30 | 6.4199 | 10.01 |
24 | 2221B 24-5-30 | 6.1945 | 9.6722 |
25 | 2211B 24-6-01 | 6.8432 | 10.6376 |
26 | 2221B 24-6-01 | 6.7699 | 10.5311 |
27 | 2211B 24-6-06 | 6.5128 | 10.1252 |
28 | 2221B 24-6-06 | 6.5522 | 10.1853 |
29 | 2211B 24-6-08 | 6.1568 | 9.5895 |
30 | 2221B 24-6-08 | 6.3137 | 9.8241 |
31 | 2211B 24-6-13 | 6.3861 | 9.9479 |
32 | 2221B 24-6-13 | 6.4425 | 10.0345 |
33 | 2211B 24-6-15 | 6.1432 | 9.5826 |
34 | 2221B 24-6-15 | 5.9925 | 9.3564 |
35 | 2211B 24-6-20 | 6.2565 | 9.7563 |
36 | 2221B 24-6-20 | 6.3465 | 9.8964 |
37 | 2211B 24-6-22 | 6.5925 | 10.2676 |
38 | 2221B 24-6-22 | 6.6562 | 10.3664 |
39 | 2211B 24-6-25 | 6.5505 | 10.1896 |
40 | 2221B 24-6-25 | 6.5317 | 10.1664 |
41 | 2211B 24-6-27 | 6.6507 | 10.3532 |
42 | 2221B 24-6-27 | 6.9731 | 10.8357 |
43 | 2211B 24-6-29 | 6.2971 | 9.8167 |
44 | 2221B 24-6-29 | 6.4543 | 10.0553 |
45 | 2211B 24-7-02 | 6.5787 | 10.2292 |
46 | 2221B 24-7-02 | 6.5440 | 10.1811 |
47 | 2211B 24-7-04 | 6.5318 | 10.1581 |
48 | 2221B 24-7-04 | 6.5203 | 10.143 |
49 | 2211B 24-7-06 | 6.8872 | 10.6905 |
50 | 2221B 24-7-06 | 6.8200 | 10.5942 |
51 | 2211B 24-7-09 | 6.4397 | 10.0182 |
52 | 2221B 24-7-09 | 6.3319 | 9.8601 |
53 | 2211B 24-7-11 | 5.8818 | 9.2 |
54 | 2221B 24-7-11 | 5.8409 | 9.1368 |
55 | 2211B 24-7-16 | 6.6162 | 10.2957 |
56 | 2221B 24-7-16 | 6.4957 | 10.1173 |
57 | 2211B 24-7-18 | 6.1803 | 9.6382 |
58 | 2221B 24-7-18 | 6.0278 | 9.409 |
59 | 2211B 24-7-20 | 6.0428 | 9.4217 |
60 | 2221B 24-7-20 | 5.9711 | 9.3155 |
61 | 2211B 24-7-23 | 6.0565 | 9.4544 |
62 | 2221B 24-7-23 | 6.0809 | 9.4929 |
63 | 2211B 24-7-25 | 6.2501 | 9.7429 |
64 | 2221B 24-7-25 | 6.2119 | 9.6872 |
65 | 2211B 24-7-27 | 6.4237 | 9.9947 |
66 | 2221B 24-7-27 | 6.3502 | 9.8881 |
67 | 2211B 24-7-30 | 6.5834 | 10.2525 |
68 | 2221B 24-7-30 | 6.4896 | 10.1129 |
69 | 2211B 24-8-1 | 6.4662 | 10.0774 |
70 | 2221B 24-8-1 | 6.4172 | 10.0057 |
71 | 2211B 24-8-3 | 7.0135 | 10.8917 |
72 | 2221B 24-8-3 | 7.4943 | 11.602 |
73 | 2211B 24-8-6 | 6.3456 | 9.8863 |
74 | 2221B 24-8-6 | 6.3810 | 9.9419 |
75 | 2211B 24-8-8 | 5.9318 | 9.2817 |
76 | 2221B 24-8-8 | 6.0294 | 9.4287 |
77 | 2211B 24-8-10 | 6.4085 | 9.9907 |
78 | 2221B 24-8-10 | 6.3699 | 9.9325 |
79 | 2211B 24-8-13 | 6.3239 | 9.8566 |
80 | 2221B 24-8-13 | 6.1951 | 9.6641 |
81 | 2211B 24-8-15 | 6.5765 | 10.24 |
82 | 2221B 24-8-15 | 6.4083 | 9.9879 |
83 | 2211B 24-8-17 | 6.4776 | 10.0762 |
84 | 2221B 24-8-17 | 6.2939 | 9.8025 |
85 | 2211B 24-8-20 | 6.3265 | 9.8392 |
86 | 2221B 24-8-20 | 6.0361 | 9.4056 |
87 | 2211B 24-8-22 | 6.5948 | 10.2563 |
88 | 2221B 24-8-22 | 6.4098 | 9.9802 |
89 | 2211B 24-8-24 | 6.6635 | 10.3508 |
90 | 2221B 24-8-24 | 6.4976 | 10.1034 |
91 | 2211B 24-8-27 | 6.3708 | 9.919 |
92 | 2221B 24-8-27 | 6.3035 | 9.82 |
93 | 2211B 24-8-29 | 6.7994 | 10.5755 |
94 | 2221B 24-8-29 | 6.7861 | 10.5548 |
95 | 2211B 24-8-31 | 6.7958 | 10.5671 |
96 | 2221B 24-8-31 | 6.6840 | 10.3998 |
表2硝基苯基础数据:
数量 | 样品 | 归一化硝基苯% | 面积百分比 硝基苯% |
1 | 2211B 24-5-4 | 93.4586 | 89.5694 |
2 | 2221B 24-5-4 | 93.4101 | 89.5087 |
3 | 2211B 24-5-7 | 92.8415 | 88.9462 |
4 | 2221B 24-5-7 | 93.3924 | 89.4868 |
5 | 2211B 24-5-7 | 93.6401 | 89.8593 |
6 | 2211B 24-5-9 | 93.5468 | 89.6066 |
7 | 2211B 24-5-11 | 93.3198 | 89.1512 |
8 | 2221B 24-5-11 | 93.2442 | 89.0444 |
9 | 2211B 24-5-14 | 93.4043 | 89.3408 |
10 | 2221B 24-5-14 | 93.6673 | 89.7708 |
11 | 2211B 24-5-16 | 93.6324 | 89.6181 |
12 | 2221B 24-5-16 | 93.6293 | 89.6304 |
13 | 2211B 24-5-18 | 93.7296 | 89.6332 |
14 | 2221B 24-5-18 | 93.6162 | 89.4891 |
15 | 2211B 24-5-21 | 93.5494 | 89.4629 |
16 | 2221B 24-5-21 | 93.4598 | 89.3597 |
17 | 2211B 24-5-23 | 93.0686 | 88.8913 |
18 | 2221B 24-5-23 | 93.2005 | 89.1149 |
19 | 2211B 24-5-25 | 93.0234 | 88.8901 |
20 | 2221B 24-5-25 | 93.1057 | 89.0248 |
21 | 2211B 24-5-28 | 92.9073 | 88.6780 |
22 | 2221B 24-5-28 | 93.0955 | 88.9839 |
23 | 2211B 24-5-30 | 93.5399 | 89.6438 |
24 | 2221B 24-5-30 | 93.7635 | 89.9834 |
25 | 2211B 24-6-01 | 93.1159 | 88.9659 |
26 | 2221B 24-6-01 | 93.1912 | 89.1001 |
27 | 2211B 24-6-06 | 93.4479 | 89.2929 |
28 | 2221B 24-6-06 | 93.4080 | 89.2450 |
29 | 2211B 24-6-08 | 93.8013 | 89.7978 |
30 | 2221B 24-6-08 | 93.6457 | 89.5600 |
31 | 2211B 24-6-13 | 93.5743 | 89.5908 |
32 | 2221B 24-6-13 | 93.5183 | 89.5262 |
33 | 2211B 24-6-15 | 93.8159 | 89.9464 |
34 | 2221B 24-6-15 | 93.9666 | 90.1753 |
35 | 2211B 24-6-20 | 93.7059 | 89.8117 |
36 | 2221B 24-6-20 | 93.6148 | 89.7218 |
37 | 2211B 24-6-22 | 93.3724 | 89.3814 |
38 | 2221B 24-6-22 | 93.3068 | 89.3150 |
39 | 2211B 24-6-25 | 93.4061 | 89.3038 |
40 | 2221B 24-6-25 | 93.4251 | 89.3747 |
41 | 2211B 24-6-27 | 93.3039 | 89.2727 |
42 | 2221B 24-6-27 | 92.9834 | 88.8075 |
43 | 2211B 24-6-29 | 93.6631 | 89.7443 |
44 | 2221B 24-6-29 | 93.5051 | 89.5358 |
45 | 2211B 24-7-02 | 93.3862 | 89.2480 |
46 | 2221B 24-7-02 | 93.4212 | 89.3327 |
47 | 2211B 24-7-04 | 93.4356 | 89.3113 |
48 | 2221B 24-7-04 | 93.4473 | 89.3464 |
49 | 2211B 24-7-06 | 93.0695 | 88.7920 |
50 | 2221B 24-7-06 | 93.1367 | 88.9235 |
51 | 2211B 24-7-09 | 93.5226 | 89.4243 |
52 | 2221B 24-7-09 | 93.6306 | 89.6146 |
53 | 2211B 24-7-11 | 94.0718 | 90.4374 |
54 | 2221B 24-7-11 | 94.1125 | 90.4852 |
55 | 2211B 24-7-16 | 93.3496 | 89.2834 |
56 | 2221B 24-7-16 | 93.4693 | 89.4797 |
57 | 2211B 24-7-18 | 93.7831 | 89.8923 |
58 | 2221B 24-7-18 | 93.9348 | 90.1203 |
59 | 2211B 24-7-20 | 93.9184 | 90.0024 |
60 | 2221B 24-7-20 | 93.9913 | 90.1270 |
61 | 2211B 24-7-23 | 93.9067 | 90.0988 |
62 | 2221B 24-7-23 | 93.8844 | 90.0825 |
63 | 2211B 24-7-25 | 93.7130 | 89.7871 |
64 | 2221B 24-7-25 | 93.7535 | 89.8625 |
65 | 2211B 24-7-27 | 93.5445 | 89.4584 |
66 | 2221B 24-7-27 | 93.6212 | 89.6015 |
67 | 2211B 24-7-30 | 93.3752 | 89.3768 |
68 | 2221B 24-7-30 | 93.4696 | 89.5246 |
69 | 2211B 24-8-1 | 93.4897 | 89.5522 |
70 | 2221B 24-8-1 | 93.5400 | 89.6423 |
71 | 2211B 24-8-3 | 92.9464 | 88.7177 |
72 | 2221B 24-8-3 | 92.4661 | 87.9825 |
73 | 2211B 24-8-6 | 93.6151 | 89.6438 |
74 | 2221B 24-8-6 | 93.5798 | 89.6136 |
75 | 2211B 24-8-8 | 94.0175 | 90.4205 |
76 | 2221B 24-8-8 | 93.9266 | 90.2767 |
77 | 2211B 24-8-10 | 93.5511 | 89.6404 |
78 | 2221B 24-8-10 | 93.5908 | 89.6958 |
79 | 2211B 24-8-13 | 93.6294 | 89.6944 |
80 | 2221B 24-8-13 | 93.7578 | 89.8946 |
81 | 2211B 24-8-15 | 93.3868 | 89.3723 |
82 | 2221B 24-8-15 | 93.5562 | 89.6220 |
83 | 2211B 24-8-17 | 93.4887 | 89.3836 |
84 | 2221B 24-8-17 | 93.6716 | 89.6686 |
85 | 2211B 24-8-20 | 93.6334 | 89.5038 |
86 | 2221B 24-8-20 | 93.9251 | 89.9552 |
87 | 2211B 24-8-22 | 93.3711 | 89.2509 |
88 | 2221B 24-8-22 | 93.5563 | 89.5318 |
89 | 2211B 24-8-24 | 93.3044 | 89.0823 |
90 | 2221B 24-8-24 | 93.4706 | 89.3307 |
91 | 2211B 24-8-27 | 93.5872 | 89.5583 |
92 | 2221B 24-8-27 | 93.6551 | 89.6757 |
93 | 2211B 24-8-29 | 93.1708 | 89.0684 |
94 | 2221B 24-8-29 | 93.1839 | 89.0807 |
95 | 2211B 24-8-31 | 93.1665 | 89.0414 |
96 | 2221B 24-8-31 | 93.2785 | 89.2034 |
表3对二硝基苯基础数据:
数量 | 样品 | 归一化 对二硝基苯% | 面积百分比 对二硝基苯% |
1 | 2211B 24-5-4 | 0.0040 | 0.0025 |
2 | 2221B 24-5-4 | 0.0021 | 0.0013 |
3 | 2211B 24-5-7 | 0.0630 | 0.0401 |
4 | 2221B 24-5-7 | 0.0059 | 0.0037 |
5 | 2211B 24-5-7 | 0.0035 | 0.0022 |
6 | 2211B 24-5-9 | 0.0016 | 0.0010 |
7 | 2211B 24-5-11 | 0.0011 | 0.0007 |
8 | 2221B 24-5-11 | 0.0011 | 0.0007 |
9 | 2211B 24-5-14 | 0.0011 | 0.0007 |
10 | 2221B 24-5-14 | 0.0012 | 0.0007 |
11 | 2211B 24-5-16 | 0.0012 | 0.0008 |
12 | 2221B 24-5-16 | 0.0012 | 0.0008 |
13 | 2211B 24-5-18 | 0.0012 | 0.0008 |
14 | 2221B 24-5-18 | 0.0012 | 0.0007 |
15 | 2211B 24-5-21 | 0.0011 | 0.0007 |
16 | 2221B 24-5-21 | 0.0011 | 0.0007 |
17 | 2211B 24-5-23 | 0.0010 | 0.0007 |
18 | 2221B 24-5-23 | 0.0010 | 0.0006 |
19 | 2211B 24-5-25 | 0.0010 | 0.0006 |
20 | 2221B 24-5-25 | 0.0009 | 0.0006 |
21 | 2211B 24-5-28 | 0.0010 | 0.0007 |
22 | 2221B 24-5-28 | 0.0011 | 0.0007 |
23 | 2211B 24-5-30 | 0.0012 | 0.0008 |
24 | 2221B 24-5-30 | 0.0013 | 0.0008 |
25 | 2211B 24-6-01 | 0.0011 | 0.0007 |
26 | 2221B 24-6-01 | 0.0010 | 0.0006 |
27 | 2211B 24-6-06 | 0.0011 | 0.0007 |
28 | 2221B 24-6-06 | 0.0010 | 0.0007 |
29 | 2211B 24-6-08 | 0.0012 | 0.0007 |
30 | 2221B 24-6-08 | 0.0011 | 0.0007 |
31 | 2211B 24-6-13 | 0.0011 | 0.0007 |
32 | 2221B 24-6-13 | 0.0010 | 0.0007 |
33 | 2211B 24-6-15 | 0.0012 | 0.0008 |
34 | 2221B 24-6-15 | 0.0012 | 0.0007 |
35 | 2211B 24-6-20 | 0.0012 | 0.0007 |
36 | 2221B 24-6-20 | 0.0012 | 0.0007 |
37 | 2211B 24-6-22 | 0.0010 | 0.0007 |
38 | 2221B 24-6-22 | 0.0011 | 0.0007 |
39 | 2211B 24-6-25 | 0.0011 | 0.0007 |
40 | 2221B 24-6-25 | 0.0011 | 0.0007 |
41 | 2211B 24-6-27 | 0.0010 | 0.0007 |
42 | 2221B 24-6-27 | 0.0010 | 0.0006 |
43 | 2211B 24-6-29 | 0.0011 | 0.0007 |
44 | 2221B 24-6-29 | 0.0012 | 0.0008 |
45 | 2211B 24-7-02 | 0.0011 | 0.0007 |
46 | 2221B 24-7-02 | 0.0011 | 0.0007 |
47 | 2211B 24-7-04 | 0.0010 | 0.0007 |
48 | 2221B 24-7-04 | 0.0010 | 0.0007 |
49 | 2211B 24-7-06 | 0.0010 | 0.0006 |
50 | 2221B 24-7-06 | 0.0010 | 0.0006 |
51 | 2211B 24-7-09 | 0.0011 | 0.0007 |
52 | 2221B 24-7-09 | 0.0011 | 0.0007 |
53 | 2211B 24-7-11 | 0.0015 | 0.0009 |
54 | 2221B 24-7-11 | 0.0014 | 0.0009 |
55 | 2211B 24-7-16 | 0.0010 | 0.0006 |
56 | 2221B 24-7-16 | 0.0010 | 0.0006 |
57 | 2211B 24-7-18 | 0.0011 | 0.0007 |
58 | 2221B 24-7-18 | 0.0011 | 0.0007 |
59 | 2211B 24-7-20 | 0.0011 | 0.0007 |
60 | 2221B 24-7-20 | 0.0010 | 0.0007 |
61 | 2211B 24-7-23 | 0.0012 | 0.0007 |
62 | 2221B 24-7-23 | 0.0011 | 0.0007 |
63 | 2211B 24-7-25 | 0.0010 | 0.0006 |
64 | 2221B 24-7-25 | 0.0009 | 0.0006 |
65 | 2211B 24-7-27 | 0.0010 | 0.0006 |
66 | 2221B 24-7-27 | 0.0009 | 0.0006 |
67 | 2211B 24-7-30 | 0.0009 | 0.0006 |
68 | 2221B 24-7-30 | 0.0009 | 0.0006 |
69 | 2211B 24-8-1 | 0.0010 | 0.0006 |
70 | 2221B 24-8-1 | 0.0010 | 0.0006 |
71 | 2211B 24-8-3 | 0.0008 | 0.0005 |
72 | 2221B 24-8-3 | 0.0008 | 0.0005 |
73 | 2211B 24-8-6 | 0.0011 | 0.0007 |
74 | 2221B 24-8-6 | 0.0011 | 0.0007 |
75 | 2211B 24-8-8 | 0.0017 | 0.0011 |
76 | 2221B 24-8-8 | 0.0014 | 0.0009 |
77 | 2211B 24-8-10 | 0.0011 | 0.0007 |
78 | 2221B 24-8-10 | 0.0011 | 0.0007 |
79 | 2211B 24-8-13 | 0.0012 | 0.0008 |
80 | 2221B 24-8-13 | 0.0012 | 0.0008 |
81 | 2211B 24-8-15 | 0.0010 | 0.0007 |
82 | 2221B 24-8-15 | 0.0010 | 0.0006 |
83 | 2211B 24-8-17 | 0.0010 | 0.0006 |
84 | 2221B 24-8-17 | 0.0010 | 0.0007 |
85 | 2211B 24-8-20 | 0.0011 | 0.0007 |
86 | 2221B 24-8-20 | 0.0010 | 0.0006 |
87 | 2211B 24-8-22 | 0.0010 | 0.0006 |
88 | 2221B 24-8-22 | 0.0010 | 0.0006 |
89 | 2211B 24-8-24 | 0.0010 | 0.0006 |
90 | 2221B 24-8-24 | 0.0009 | 0.0006 |
91 | 2211B 24-8-27 | 0.0011 | 0.0007 |
92 | 2221B 24-8-27 | 0.0011 | 0.0007 |
93 | 2211B 24-8-29 | 0.0010 | 0.0006 |
94 | 2221B 24-8-29 | 0.0010 | 0.0006 |
95 | 2211B 24-8-31 | 0.0011 | 0.0007 |
96 | 2221B 24-8-31 | 0.0010 | 0.0007 |
表4间二硝基苯基础数据:
数量 | 样品 | 归一化 间二硝基苯% | 面积百分比 间二硝基苯% |
1 | 2211B 24-5-4 | 0.0227 | 0.0145 |
2 | 2221B 24-5-4 | 0.0207 | 0.0132 |
3 | 2211B 24-5-7 | 0.0286 | 0.0182 |
4 | 2221B 24-5-7 | 0.0225 | 0.0143 |
5 | 2211B 24-5-7 | 0.0238 | 0.0152 |
6 | 2211B 24-5-9 | 0.0242 | 0.0154 |
7 | 2211B 24-5-11 | 0.0218 | 0.0138 |
8 | 2221B 24-5-11 | 0.0220 | 0.0140 |
9 | 2211B 24-5-14 | 0.0243 | 0.0155 |
10 | 2221B 24-5-14 | 0.0250 | 0.0159 |
11 | 2211B 24-5-16 | 0.0247 | 0.0157 |
12 | 2221B 24-5-16 | 0.0241 | 0.0153 |
13 | 2211B 24-5-18 | 0.0245 | 0.0156 |
14 | 2221B 24-5-18 | 0.0236 | 0.0150 |
15 | 2211B 24-5-21 | 0.0230 | 0.0146 |
16 | 2221B 24-5-21 | 0.0225 | 0.0143 |
17 | 2211B 24-5-23 | 0.0217 | 0.0137 |
18 | 2221B 24-5-23 | 0.0219 | 0.0139 |
19 | 2211B 24-5-25 | 0.0224 | 0.0142 |
20 | 2221B 24-5-25 | 0.0215 | 0.0137 |
21 | 2211B 24-5-28 | 0.0221 | 0.0140 |
22 | 2221B 24-5-28 | 0.0224 | 0.0142 |
23 | 2211B 24-5-30 | 0.0259 | 0.0165 |
24 | 2221B 24-5-30 | 0.0272 | 0.0173 |
25 | 2211B 24-6-01 | 0.0233 | 0.0148 |
26 | 2221B 24-6-01 | 0.0226 | 0.0144 |
27 | 2211B 24-6-06 | 0.0231 | 0.0146 |
28 | 2221B 24-6-06 | 0.0231 | 0.0147 |
29 | 2211B 24-6-08 | 0.0246 | 0.0157 |
30 | 2221B 24-6-08 | 0.0244 | 0.0155 |
31 | 2211B 24-6-13 | 0.0234 | 0.0149 |
32 | 2221B 24-6-13 | 0.0233 | 0.0148 |
33 | 2211B 24-6-15 | 0.0259 | 0.0165 |
34 | 2221B 24-6-15 | 0.0264 | 0.0168 |
35 | 2211B 24-6-20 | 0.0245 | 0.0156 |
36 | 2221B 24-6-20 | 0.0257 | 0.0164 |
37 | 2211B 24-6-22 | 0.0217 | 0.0138 |
38 | 2221B 24-6-22 | 0.0237 | 0.0150 |
39 | 2211B 24-6-25 | 0.0233 | 0.0148 |
40 | 2221B 24-6-25 | 0.0236 | 0.0150 |
41 | 2211B 24-6-27 | 0.0234 | 0.0149 |
42 | 2221B 24-6-27 | 0.0221 | 0.014 |
43 | 2211B 24-6-29 | 0.0254 | 0.0162 |
44 | 2221B 24-6-29 | 0.0261 | 0.0166 |
45 | 2211B 24-7-02 | 0.0234 | 0.0148 |
46 | 2221B 24-7-02 | 0.0230 | 0.0146 |
47 | 2211B 24-7-04 | 0.0233 | 0.0148 |
48 | 2221B 24-7-04 | 0.0229 | 0.0146 |
49 | 2211B 24-7-06 | 0.0220 | 0.0139 |
50 | 2221B 24-7-06 | 0.0222 | 0.0141 |
51 | 2211B 24-7-09 | 0.0237 | 0.015 |
52 | 2221B 24-7-09 | 0.0239 | 0.0152 |
53 | 2211B 24-7-11 | 0.0304 | 0.0194 |
54 | 2221B 24-7-11 | 0.0301 | 0.0192 |
55 | 2211B 24-7-16 | 0.0205 | 0.013 |
56 | 2221B 24-7-16 | 0.0218 | 0.0138 |
57 | 2211B 24-7-18 | 0.0243 | 0.0155 |
58 | 2221B 24-7-18 | 0.0250 | 0.0159 |
59 | 2211B 24-7-20 | 0.0232 | 0.0148 |
60 | 2221B 24-7-20 | 0.0231 | 0.0147 |
61 | 2211B 24-7-23 | 0.0241 | 0.0153 |
62 | 2221B 24-7-23 | 0.0231 | 0.0147 |
63 | 2211B 24-7-25 | 0.0226 | 0.0144 |
64 | 2221B 24-7-25 | 0.0215 | 0.0137 |
65 | 2211B 24-7-27 | 0.0222 | 0.0141 |
66 | 2221B 24-7-27 | 0.0202 | 0.0128 |
67 | 2211B 24-7-30 | 0.0206 | 0.0131 |
68 | 2221B 24-7-30 | 0.0202 | 0.0129 |
69 | 2211B 24-8-1 | 0.0224 | 0.0143 |
70 | 2221B 24-8-1 | 0.0217 | 0.0138 |
71 | 2211B 24-8-3 | 0.0186 | 0.0118 |
72 | 2221B 24-8-3 | 0.0184 | 0.0116 |
73 | 2211B 24-8-6 | 0.0240 | 0.0153 |
74 | 2221B 24-8-6 | 0.0240 | 0.0153 |
75 | 2211B 24-8-8 | 0.0338 | 0.0216 |
76 | 2221B 24-8-8 | 0.0284 | 0.0181 |
77 | 2211B 24-8-10 | 0.0245 | 0.0156 |
78 | 2221B 24-8-10 | 0.0236 | 0.0150 |
79 | 2211B 24-8-13 | 0.0262 | 0.0167 |
80 | 2221B 24-8-13 | 0.0268 | 0.0171 |
81 | 2211B 24-8-15 | 0.0232 | 0.0147 |
82 | 2221B 24-8-15 | 0.0223 | 0.0142 |
83 | 2211B 24-8-17 | 0.0226 | 0.0143 |
84 | 2221B 24-8-17 | 0.0232 | 0.0147 |
85 | 2211B 24-8-20 | 0.0232 | 0.0147 |
86 | 2221B 24-8-20 | 0.0222 | 0.0141 |
87 | 2211B 24-8-22 | 0.0224 | 0.0142 |
88 | 2221B 24-8-22 | 0.0222 | 0.0141 |
89 | 2211B 24-8-24 | 0.0213 | 0.0135 |
90 | 2221B 24-8-24 | 0.0211 | 0.0134 |
91 | 2211B 24-8-27 | 0.024 | 0.0153 |
92 | 2221B 24-8-27 | 0.0237 | 0.0151 |
93 | 2211B 24-8-29 | 0.0221 | 0.014 |
94 | 2221B 24-8-29 | 0.0223 | 0.0142 |
95 | 2211B 24-8-31 | 0.0242 | 0.0154 |
96 | 2221B 24-8-31 | 0.0240 | 0.0153 |
表5邻二硝基苯基础数据:
数量 | 样品 | 归一化 邻二硝基苯% | 面积百分比 邻二硝基苯% |
1 | 2211B 24-5-4 | 0.0045 | 0.0028 |
2 | 2221B 24-5-4 | 0.0035 | 0.0022 |
3 | 2211B 24-5-7 | 0.0124 | 0.0077 |
4 | 2221B 24-5-7 | 0.0039 | 0.0024 |
5 | 2211B 24-5-7 | 0.0044 | 0.0028 |
6 | 2211B 24-5-9 | 0.0039 | 0.0025 |
7 | 2211B 24-5-11 | 0.0034 | 0.0021 |
8 | 2221B 24-5-11 | 0.0033 | 0.0021 |
9 | 2211B 24-5-14 | 0.0038 | 0.0024 |
10 | 2221B 24-5-14 | 0.0038 | 0.0024 |
11 | 2211B 24-5-16 | 0.0037 | 0.0023 |
12 | 2221B 24-5-16 | 0.0036 | 0.0023 |
13 | 2211B 24-5-18 | 0.0038 | 0.0024 |
14 | 2221B 24-5-18 | 0.0036 | 0.0022 |
15 | 2211B 24-5-21 | 0.0037 | 0.0023 |
16 | 2221B 24-5-21 | 0.0034 | 0.0021 |
17 | 2211B 24-5-23 | 0.0033 | 0.0021 |
18 | 2221B 24-5-23 | 0.0033 | 0.0021 |
19 | 2211B 24-5-25 | 0.0034 | 0.0021 |
20 | 2221B 24-5-25 | 0.0033 | 0.0020 |
21 | 2211B 24-5-28 | 0.0034 | 0.0021 |
22 | 2221B 24-5-28 | 0.0034 | 0.0021 |
23 | 2211B 24-5-30 | 0.0040 | 0.0025 |
24 | 2221B 24-5-30 | 0.0041 | 0.0026 |
25 | 2211B 24-6-01 | 0.0035 | 0.0022 |
26 | 2221B 24-6-01 | 0.0034 | 0.0021 |
27 | 2211B 24-6-06 | 0.0035 | 0.0022 |
28 | 2221B 24-6-06 | 0.0035 | 0.0022 |
29 | 2211B 24-6-08 | 0.0038 | 0.0024 |
30 | 2221B 24-6-08 | 0.0037 | 0.0023 |
31 | 2211B 24-6-13 | 0.0036 | 0.0023 |
32 | 2221B 24-6-13 | 0.0035 | 0.0022 |
33 | 2211B 24-6-15 | 0.0040 | 0.0025 |
34 | 2221B 24-6-15 | 0.0040 | 0.0025 |
35 | 2211B 24-6-20 | 0.0037 | 0.0023 |
36 | 2221B 24-6-20 | 0.0039 | 0.0024 |
37 | 2211B 24-6-22 | 0.0033 | 0.0021 |
38 | 2221B 24-6-22 | 0.0036 | 0.0022 |
39 | 2211B 24-6-25 | 0.0037 | 0.0023 |
40 | 2221B 24-6-25 | 0.0036 | 0.0022 |
41 | 2211B 24-6-27 | 0.0036 | 0.0022 |
42 | 2221B 24-6-27 | 0.0033 | 0.0021 |
43 | 2211B 24-6-29 | 0.0039 | 0.0024 |
44 | 2221B 24-6-29 | 0.0039 | 0.0025 |
45 | 2211B 24-7-02 | 0.0036 | 0.0022 |
46 | 2221B 24-7-02 | 0.0035 | 0.0022 |
47 | 2211B 24-7-04 | 0.0035 | 0.0022 |
48 | 2221B 24-7-04 | 0.0035 | 0.0022 |
49 | 2211B 24-7-06 | 0.0033 | 0.0021 |
50 | 2221B 24-7-06 | 0.0033 | 0.0021 |
51 | 2211B 24-7-09 | 0.0037 | 0.0023 |
52 | 2221B 24-7-09 | 0.0036 | 0.0023 |
53 | 2211B 24-7-11 | 0.0048 | 0.003 |
54 | 2221B 24-7-11 | 0.0045 | 0.0029 |
55 | 2211B 24-7-16 | 0.0033 | 0.0020 |
56 | 2221B 24-7-16 | 0.0033 | 0.0021 |
57 | 2211B 24-7-18 | 0.0037 | 0.0023 |
58 | 2221B 24-7-18 | 0.0038 | 0.0024 |
59 | 2211B 24-7-20 | 0.0035 | 0.0022 |
60 | 2221B 24-7-20 | 0.0035 | 0.0022 |
61 | 2211B 24-7-23 | 0.0038 | 0.0024 |
62 | 2221B 24-7-23 | 0.0035 | 0.0022 |
63 | 2211B 24-7-25 | 0.0035 | 0.0022 |
64 | 2221B 24-7-25 | 0.0033 | 0.0020 |
65 | 2211B 24-7-27 | 0.0034 | 0.0021 |
66 | 2221B 24-7-27 | 0.0030 | 0.0019 |
67 | 2211B 24-7-30 | 0.0031 | 0.0019 |
68 | 2221B 24-7-30 | 0.0031 | 0.0019 |
69 | 2211B 24-8-1 | 0.0034 | 0.0021 |
70 | 2221B 24-8-1 | 0.0033 | 0.0021 |
71 | 2211B 24-8-3 | 0.0028 | 0.0018 |
72 | 2221B 24-8-3 | 0.0028 | 0.0017 |
73 | 2211B 24-8-6 | 0.0038 | 0.0024 |
74 | 2221B 24-8-6 | 0.0036 | 0.0023 |
75 | 2211B 24-8-8 | 0.0051 | 0.0032 |
76 | 2221B 24-8-8 | 0.0043 | 0.0027 |
77 | 2211B 24-8-10 | 0.0037 | 0.0023 |
78 | 2221B 24-8-10 | 0.0036 | 0.0022 |
79 | 2211B 24-8-13 | 0.0042 | 0.0026 |
80 | 2221B 24-8-13 | 0.0041 | 0.0026 |
81 | 2211B 24-8-15 | 0.0035 | 0.0022 |
82 | 2221B 24-8-15 | 0.0034 | 0.0021 |
83 | 2211B 24-8-17 | 0.0034 | 0.0021 |
84 | 2221B 24-8-17 | 0.0035 | 0.0022 |
85 | 2211B 24-8-20 | 0.0037 | 0.0023 |
86 | 2221B 24-8-20 | 0.0034 | 0.0021 |
87 | 2211B 24-8-22 | 0.0034 | 0.0021 |
88 | 2221B 24-8-22 | 0.0034 | 0.0021 |
89 | 2211B 24-8-24 | 0.0033 | 0.0020 |
90 | 2221B 24-8-24 | 0.0032 | 0.0020 |
91 | 2211B 24-8-27 | 0.0039 | 0.0024 |
92 | 2221B 24-8-27 | 0.0036 | 0.0023 |
93 | 2211B 24-8-29 | 0.0034 | 0.0021 |
94 | 2221B 24-8-29 | 0.0034 | 0.0021 |
95 | 2211B 24-8-31 | 0.0037 | 0.0023 |
96 | 2221B 24-8-31 | 0.0037 | 0.0023 |
表6 采集方法操作条件
柱箱温度 | 60℃ |
检测器温度 | 260℃ |
进样口温度 | 260℃ |
进样量 | 0.2uL |
载气 | 高纯氮气 |
色谱柱1 | 模式:恒定流量 柱流量:2.3mL/min |
分流比 | 15:1 |
隔垫吹扫流量 | 3mL/min |
尾吹气流量 | 30mL/min |
程序升温 | 60℃保持1min, 以20℃/min的速率升温到230℃保持5min, 总运行时间12 min |
助燃气 燃气 | 空气流量400mL/min 氢气流量35mL/min |
表7 实验用试剂
试剂 | 厂家 |
苯 | AR,国药 |
硝基苯 | 自产 |
对二硝基苯 | AR,国药 |
间二硝基苯 | AR,国药 |
邻二硝基苯 | AR,国药 |
依据线性模型的原理,将归一化和面积百分比法组分含量之间的关,进行线性模型的拟合,利用拟合方程,预测面积百分比法组分含量所对应的归一化法组分含量。
图8 两种分析方法苯数据趋势图
图9 两种分析方法硝基苯数据趋势图
图10 两种分析方法对二硝基苯数据趋势图
图11 两种分析方法间二硝基苯数据趋势图
图12 两种分析方法邻二硝基苯数据趋势图
图13两种分析方法苯关系显著 P<0.05
图14两种分析方法硝基苯关系显著 P<0.05
图15两种分析方法对二硝基苯关系显著 P<0.05
图16两种分析方法间二硝基苯关系显著 P<0.05
图17两种分析方法邻二硝基苯关系显著 P<0.05
表6 二次方法验证数据
样品 | 归一化苯% | 模型预测苯% | 相对偏差% |
2211B 23-10-3 | 5.7582 | 5.8402 | 0.71 |
2221B 23-10-3 | 5.6881 | 5.7676 | 0.69 |
2211B 23-10-3 | 5.6683 | 5.7494 | 0.71 |
2211B 23-10-3 | 6.0755 | 6.1702 | 0.77 |
2211B 23-10-10 | 6.2488 | 6.3369 | 0.70 |
2221B 23-10-10 | 6.3722 | 6.4606 | 0.69 |
2211B 23-10-12 | 6.1903 | 6.2727 | 0.66 |
2221B 23-10-12 | 5.9630 | 6.0242 | 0.51 |
2211B 23-10-14 | 6.3197 | 6.2912 | -0.23 |
2221B 23-10-14 | 6.7157 | 6.6801 | -0.27 |
2211B 23-10-17 | 6.7092 | 6.7962 | 0.64 |
2221B 23-10-17 | 6.7882 | 6.8744 | 0.63 |
2211B 23-10-21 | 6.5743 | 6.6609 | 0.65 |
2221B 23-10-21 | 6.7241 | 6.8104 | 0.64 |
2211B 23-10-24 | 6.3118 | 6.3931 | 0.64 |
2221B 23-10-24 | 6.7011 | 6.7829 | 0.61 |
2211B 24-9-3 | 6.8475 | 6.8429 | -0.03 |
2221B 24-9-3 | 6.7692 | 6.7653 | -0.03 |
2211B 24-9-5 | 6.5587 | 6.5538 | -0.04 |
2221B 24-9-5 | 6.4825 | 6.4799 | -0.02 |
2211B 24-9-10 | 6.3276 | 6.3124 | -0.12 |
2221B 24-9-10 | 6.3037 | 6.2877 | -0.13 |
2211B 24-9-12 | 6.4502 | 6.4457 | -0.03 |
2221B 24-9-12 | 6.3515 | 6.3473 | -0.03 |
2211B 24-9-14 | 6.0616 | 6.0492 | -0.10 |
2221B 24-9-14 | 5.978 | 5.9646 | -0.11 |
2211B 24-9-17 | 6.4987 | 6.4757 | -0.18 |
2221B 24-9-17 | 6.4736 | 6.4491 | -0.19 |
2211B 24-9-19 | 6.5184 | 6.5081 | -0.08 |
2221B 24-9-19 | 6.4827 | 6.4672 | -0.12 |
表7 二次方法验证数据
样品 | 归一化硝基苯% | 模型预测 硝基苯% | 相对偏差% |
2211B 23-10-3 | 94.2023 | 94.0374 | -0.09 |
2221B 23-10-3 | 94.2772 | 94.0995 | -0.09 |
2211B 23-10-3 | 94.2961 | 94.1388 | -0.08 |
2211B 23-10-3 | 93.8937 | 93.7949 | -0.05 |
2211B 23-10-10 | 93.7232 | 93.5370 | -0.10 |
2221B 23-10-10 | 93.6006 | 93.4033 | -0.11 |
2211B 23-10-12 | 93.7744 | 93.5445 | -0.12 |
2221B 23-10-12 | 94.0029 | 93.5970 | -0.22 |
2211B 23-10-14 | 93.6375 | 93.3597 | -0.15 |
2221B 23-10-14 | 93.2574 | 92.9425 | -0.17 |
2211B 23-10-17 | 93.2641 | 93.0291 | -0.13 |
2221B 23-10-17 | 93.1853 | 92.9398 | -0.13 |
2211B 23-10-21 | 93.4016 | 93.1706 | -0.12 |
2221B 23-10-21 | 93.2543 | 93.0110 | -0.13 |
2211B 23-10-24 | 93.6640 | 93.4068 | -0.14 |
2221B 23-10-24 | 93.2779 | 92.9960 | -0.15 |
2211B 24-9-3 | 93.1127 | 93.0819 | -0.02 |
2221B 24-9-3 | 93.1909 | 93.1610 | -0.02 |
2211B 24-9-5 | 93.4042 | 93.3529 | -0.03 |
2221B 24-9-5 | 93.4813 | 93.4475 | -0.02 |
2211B 24-9-10 | 93.6347 | 93.4797 | -0.08 |
2221B 24-9-10 | 93.6596 | 93.4957 | -0.09 |
2211B 24-9-12 | 93.5027 | 93.4542 | -0.03 |
2221B 24-9-12 | 93.6021 | 93.5540 | -0.03 |
2211B 24-9-14 | 93.9035 | 93.7686 | -0.07 |
2221B 24-9-14 | 93.9874 | 93.8432 | -0.08 |
2211B 24-9-17 | 93.4713 | 93.2511 | -0.12 |
2221B 24-9-17 | 93.497 | 93.2610 | -0.13 |
2211B 24-9-19 | 93.4466 | 93.3441 | -0.05 |
2221B 24-9-19 | 93.4824 | 93.3316 | -0.08 |
表8 二次方法验证数据
样品 | 归一化 对二硝基苯% | 模型预测 对二硝基苯% | 相对偏差% |
2211B 23-10-3 | 0.0020 | 0.0021 | 3.35 |
2221B 23-10-3 | 0.0024 | 0.0026 | 4.00 |
2211B 23-10-3 | 0.0020 | 0.0021 | 2.90 |
2211B 23-10-3 | 0.0019 | 0.0021 | 4.48 |
2211B 23-10-10 | 0.0015 | 0.0016 | 4.47 |
2221B 23-10-10 | 0.0017 | 0.0018 | 3.83 |
2211B 23-10-12 | 0.0013 | 0.0014 | 4.99 |
2221B 23-10-12 | 0.0017 | 0.0018 | 2.70 |
2211B 23-10-14 | 0.0026 | 0.0026 | 0.24 |
2221B 23-10-14 | 0.0023 | 0.0023 | -0.55 |
2211B 23-10-17 | 0.0013 | 0.0014 | 2.42 |
2221B 23-10-17 | 0.0015 | 0.0016 | 3.40 |
2211B 23-10-21 | 0.0012 | 0.0013 | 3.80 |
2221B 23-10-21 | 0.0014 | 0.0015 | 3.27 |
2211B 23-10-24 | 0.0012 | 0.0013 | 2.49 |
2221B 23-10-24 | 0.0014 | 0.0015 | 2.89 |
2211B 24-9-3 | 0.0011 | 0.0011 | 0.05 |
2221B 24-9-3 | 0.0011 | 0.0011 | 0.05 |
2211B 24-9-5 | 0.0011 | 0.0011 | 0.05 |
2221B 24-9-5 | 0.0010 | 0.0011 | 4.82 |
2211B 24-9-10 | 0.0010 | 0.0009 | -2.95 |
2221B 24-9-10 | 0.0010 | 0.0009 | -2.95 |
2211B 24-9-12 | 0.0011 | 0.0011 | 0.05 |
2221B 24-9-12 | 0.0010 | 0.0009 | -2.95 |
2211B 24-9-14 | 0.0011 | 0.0011 | 0.05 |
2221B 24-9-14 | 0.0011 | 0.0011 | 0.05 |
2211B 24-9-17 | 0.0009 | 0.0009 | 2.31 |
2221B 24-9-17 | 0.0009 | 0.0009 | 2.31 |
2211B 24-9-19 | 0.0009 | 0.0009 | 2.31 |
2221B 24-9-19 | 0.0009 | 0.0009 | 2.31 |
表9 二次方法验证数据
样品 | 归一化 间二硝基苯% | 模型预测 间二硝基苯% | 相对偏差% |
2211B 23-10-3 | 0.0264 | 0.0273 | 1.67 |
2221B 23-10-3 | 0.0242 | 0.0251 | 1.74 |
2211B 23-10-3 | 0.0260 | 0.0270 | 1.81 |
2211B 23-10-3 | 0.0233 | 0.0242 | 1.85 |
2211B 23-10-10 | 0.0198 | 0.0206 | 1.91 |
2221B 23-10-10 | 0.0195 | 0.0202 | 1.76 |
2211B 23-10-12 | 0.0229 | 0.0237 | 1.67 |
2221B 23-10-12 | 0.0213 | 0.0220 | 1.54 |
2211B 23-10-14 | 0.0191 | 0.0191 | -0.04 |
2221B 23-10-14 | 0.0192 | 0.0191 | -0.27 |
2211B 23-10-17 | 0.0169 | 0.0175 | 1.65 |
2221B 23-10-17 | 0.0163 | 0.0169 | 1.93 |
2211B 23-10-21 | 0.0171 | 0.0177 | 1.77 |
2221B 23-10-21 | 0.0161 | 0.0167 | 1.77 |
2211B 23-10-24 | 0.0175 | 0.0182 | 1.97 |
2221B 23-10-24 | 0.0158 | 0.0163 | 1.68 |
2211B 24-9-3 | 0.0243 | 0.0242 | -0.18 |
2221B 24-9-3 | 0.0245 | 0.0245 | 0.04 |
2211B 24-9-5 | 0.0238 | 0.0237 | -0.11 |
2221B 24-9-5 | 0.0231 | 0.0231 | 0.06 |
2211B 24-9-10 | 0.0236 | 0.0236 | -0.01 |
2221B 24-9-10 | 0.0227 | 0.0227 | -0.08 |
2211B 24-9-12 | 0.0238 | 0.0237 | -0.11 |
2221B 24-9-12 | 0.0233 | 0.0233 | -0.04 |
2211B 24-9-14 | 0.0252 | 0.0251 | -0.12 |
2221B 24-9-14 | 0.025 | 0.0250 | -0.03 |
2211B 24-9-17 | 0.0213 | 0.0213 | -0.07 |
2221B 24-9-17 | 0.0209 | 0.0208 | -0.22 |
2211B 24-9-19 | 0.0210 | 0.0210 | -0.09 |
2221B 24-9-19 | 0.0209 | 0.0210 | 0.15 |
表10 二次方法验证数据
样品 | 归一化 邻二硝基苯% | 模型预测 邻二硝基苯% | 相对偏差% |
2211B 23-10-3 | 0.0044 | 0.0045 | 1.56 |
2221B 23-10-3 | 0.0040 | 0.0041 | 1.30 |
2211B 23-10-3 | 0.0042 | 0.0043 | 1.13 |
2211B 23-10-3 | 0.0038 | 0.0039 | 1.71 |
2211B 23-10-10 | 0.0035 | 0.0036 | 1.39 |
2221B 23-10-10 | 0.0033 | 0.0034 | 1.66 |
2211B 23-10-12 | 0.0039 | 0.0040 | 0.98 |
2221B 23-10-12 | 0.0036 | 0.0037 | 1.05 |
2211B 23-10-14 | 0.0031 | 0.0031 | 0.38 |
2221B 23-10-14 | 0.0032 | 0.0032 | 1.46 |
2211B 23-10-17 | 0.0031 | 0.0031 | 0.61 |
2221B 23-10-17 | 0.0028 | 0.0029 | 0.92 |
2211B 23-10-21 | 0.0029 | 0.0030 | 1.24 |
2221B 23-10-21 | 0.0027 | 0.0028 | 1.78 |
2211B 23-10-24 | 0.0032 | 0.0032 | 0.44 |
2221B 23-10-24 | 0.0027 | 0.0027 | 0.69 |
2211B 24-9-3 | 0.0039 | 0.0038 | -0.79 |
2221B 24-9-3 | 0.0037 | 0.0037 | -0.28 |
2211B 24-9-5 | 0.0036 | 0.0037 | 1.09 |
2221B 24-9-5 | 0.0035 | 0.0035 | 0.30 |
2211B 24-9-10 | 0.0037 | 0.0037 | -0.28 |
2221B 24-9-10 | 0.0035 | 0.0035 | 0.30 |
2211B 24-9-12 | 0.0036 | 0.0037 | 1.09 |
2221B 24-9-12 | 0.0036 | 0.0035 | -1.11 |
2211B 24-9-14 | 0.0039 | 0.0038 | -0.79 |
2221B 24-9-14 | 0.0038 | 0.0038 | 0.51 |
2211B 24-9-17 | 0.0034 | 0.0034 | -0.56 |
2221B 24-9-17 | 0.0032 | 0.0032 | 0.05 |
2211B 24-9-19 | 0.0032 | 0.0032 | 0.05 |
2221B 24-9-19 | 0.0032 | 0.0032 | 0.05 |
Ins_c5930403
第5楼2024/10/06
可能因为前面的历史数据,没有用校正归一,而是简单的面积归一。这样校正归一与面积归一曲线拟合,就可以得到以前校正归一曲线时的数据。
xx_dxd_xx
第6楼2024/10/07
这样说也是说不通的。校正归一化和面积百分比是两种算法,而不是两种测量方法,使用的原始色谱数据都是一样的,只是处理数据的公式有差别。如果原来的没有用校正归一化计算,只需要测出校正因子之后重新计算一遍就够了。这里的问题实际上就回到了我先提到的,关键是要验证校正因子的一致性。早期的实验条件与现在的是否一致,是否具有相同的校正因子?不同的三台仪器是否完全一致,是否具有相同的校正因子?
lvyan900430
第7楼2024/10/09
对于这位老师提出的质疑我们表示感谢,本文的研究出发点可能没那么复杂,主要是以下原因:
1、目前硝基苯产品的国标方法采用面积百分比法进行计算,但最早的时候采用归一化法进行计算,我们原先所有的计算都是归一化法,生产过程中的粗硝仍然沿用原先的归一进行计算,我们也尝试让生产接受国标使用的面积百分比法的数据,但是两者间数值差距较大,生产回复无法满足生产控制,需要我们沿用归一的方法,粗硝和精硝采用两种读数方法在分析过程中可能会产生读数方法选用错误的情况,造成客诉,所以我们迫切想找到一个方法让生产接受,所以尝试找到两组数据间的差值系数,供生产参考;
2、其次归一法读数需要产品中的每种杂质都在谱图上出峰,所以在正常分析过程中我们会增加分析试剂品种,同时要做出每种杂质的校正因子,其实还是会影响工作效率的;
3、对于提出的三台数据我们明白仪器间的差异,所以在研究讨论时我们都是单独进行分析研究的;
4、对于文中的不同物质两组数据间的比对来看,硝基苯两组数据间的线性差异比其他的物质都要大,因此可能在分析过程中不仅存在仪器的精密度差异,可能还有其他的原因造成这一现象,这也是我们后续需要再去探索的点;
感谢老师提出的疑问,有问题我们也可以多交流,非常感谢!
xx_dxd_xx
第8楼2024/10/09
我也不是想说什么复杂的问题,而是觉得你把简单问题搞复杂了,反而给自己找了麻烦。
我主要就是想说明,面积百分比和你们以前用的校正归一化,其实是同一种方法,至少在测量方法和原始数据上是完全一样的,差异只在于最后的计算。校正的归一化,实际上就是测定每一种组分的校正因子,让后带入归一化公式。而面积百分比,实际上就是假设校正因子都是1,把1带入归一化公式。所以面积百分比实际上是对校正归一化的简化形式,或者简单说是一个偷懒的方法。
至于说最后结果,你完全可以建立两个后处理方法,分别对应内部标准的校正归一化,和对应国标的面积百分比。后处理方法不影响原始谱图,想要用哪一种方法,调出数据再处理一遍就完事了,完全不存在新方法旧方法的问题。甚至你还可以一张图出两个报告,对外给国标报告,对内给校正归一化报告。
这种简化或者近似是有条件的,一是各种成分的响应接近,可以近似把校正因子当成1,二是杂质含量很低,近似当成1算也没多大误差。产品的国标按面积百分比,就是因为产品杂质少,符合第二条,所以可以做近视和简化。粗硝基苯不能用面积百分比而必须用校正归一化,是因为里面主要杂质是苯,两条都不符合,所以不能简化和近视。实际上,你们生产中并不一定要测所有的校正因子,只要以硝基苯为参比物,测出苯的校正因子就足够了,其他杂质假设与硝基苯一样当做1计算,这种误差其实非常小。你可以对比计算试一下。