内标对比标准曲线法与标准加入对比法的误差分析

Study on the errors within the method of the calibration curve containing an internal correction standard and in the method of the adding standard with an internal correction standard

目的对内标对比标准曲线法与标准加入对比法的原理与误差进行分析。方法以相对峰面积为指标 ,利用偏微分原理对二种方法进行误差分析。结果对于内标对比标准曲线法在Ai/Ar=0 3～ 3 0区间 ,标准曲线斜率B(b)较大而可获得较高灵敏度。Ai/Ar=a +b时 ,结果误差较小 ;样品相对峰面积越大及其相对测量误差越小 ,以及a越小时 ,分析误差越小。对于标准加入对比法得到了标准加入曲线不通过原点时的定量计算公式 ;当B与b的差值越小 ,或横轴截距 -A/B与 -a/b差值越大 ,以及测定相对峰面积的误差越小时 ,可使分析相对误差越小。结论两种方法在CE定量分析中应用可行 。

Objective To probe the principles and the errors of the method of the calibration curve and the method of the adding standard in CE,all with an internal correction standard. Method When the relative area was chosen as a parameter,the errors within the two kinds of methods were analyzed by using micro-divided knowledge. Results When the relative area(A i/A r)varied from 0.3 to 30,or B (b) is very high, the results have small errors. As A i/A r=a+b, the lowest error comes out. Besides a high relative area and a low relative error in it,the lower value also resulted in slight error in the method of the calibration curve with an internal correction standard. When the calibration curve was added to an internal correction standard did not pass through the zero point,both the quantitative formulas and the error analyses were given. If the value of (B-b) is much lower, also the relative error of the relative area is less, or the value of (A/B-a/b) is much higher, the result can be of slight error. Conclusions It is possible for the two kinds of quantitative methods of CE to be employed in practice, especially, in the case of loading an indefinite injection volume in a run. All the rules suit the quantitative analyses of gas chromatography and high performance liquid chromatography.