A comparative study of novel spectrophotometric methods for simultaneous determination of nitroaniline isomers in their binary mixtures with highly severe overlapping spectra.

In the present work, four simple and economic spectrophotometric methods, namely constant center (CC), ratio difference (RD), H-point standard addition method (HPSAM), and ratio H-point standard addition method (RHPSAM) were employed for the simultaneous determination of meta and para-nitroaniline with severely overlapping spectra without unitizing the preliminary physical separation techniques. In each method, the parameters affecting the resolution of the spectra were optimized to determine the cited isomers in a binary mixture with a high accuracy. Under the optimized conditions, the results obtained showed that from cited methods used, the CC and RD methods have the least errors in determination of the concentration of highly spectral overlapping species. The mean percentage recovery values for the binary mixture of meta- and para-nitroaniline were found to be 95.98 and 98.78 using the RD method, and 101.85 and 100.23 using the CC method, respectively. For comparison of the powerful multivariate methods including the principal component regression (PCR) and partial least squares (PLS) were also applied. The mean percentage recovery values for the binary mixtures of the cited isomers were found to be 101.62 and 101.47 using the PCR method, and 101.00 and 101.36 using the PLS method, respectively. A statistical comparison of the methods demonstrated that there was no significant difference between the RD, CC, PCR, and PLS methods and the reported HPLC method regarding both accuracy and precision. The proposed methods have an admissible precision and accuracy for determination of the two isomers in their binary mixtures in tap water as a real sample.