The present studies were composed of three parts; i) deconvolution study of gas chromtographic peaks for mesuring of secondary isotope effects or for analyzing products during photochemical raction, ii) measurement of secondary isotope effects directly by using gas chromatography, iii) photochemistry of vinylbromide.
In Part A, a simple and improved procedure to resolve an overlapped asymmetric chromatogram into its component peaks has been proposed. The overlapped asymmetric peak profile was assumed to be a convolution of its component peaks, which were characterized by an exponentially modified Gaussian (EMG). The overlapped EMG function was simplified by using its derivative chromatogram and a new technique for initial guessing was suggested. The simulation study showed that the present techniques were practical for implimenation on microcomputer. This techinques were confirmed its validity by comparing with experimental observations and its recovering abilities were found to be no more than 1.6% of deviations from true values and 2.2% in standard deviation throughout the study.
In Part B, the inverse secondary isotope effects of Rh(I)-$C_2H_4$ and Rh (I)-$C_2H_3D$ were measured directly using a GC column of dicarbonyl-rhodium (I)-3-trifluoroacetyl-1R-camphorate (RHC) in squalane solution and were also deduced from a reduced partition function using harmonic vibrational frequencies of Rh(I)-$C_2H_4$ and Rh(I)-$C_2H_3D$ complexes. The observed isotope effects were reasonable agreement with the deduced ones from the reduced partition function. Thermodynamic date of the inverse isotope effect were $\triangle_{D,H}\triangle H = -469 \pm 12 J mol^{-1}$ and $\triangle_{D,H}\triangle S = -0,975 \pm 0.017 J mol^{-1} K^{-1}$, respectively. From the vibrational frequencies assignment of RHC-$C_2H_4$, we have correlated the separation factors in the complexation $GC_s$ with the extent of $C_2H_4$ rehybridization for complexation.
In Part C, The photolysis of gas phase vinyl bromide was carried out at 163.4 and 184.9 nm. The major reaction products were analyzing by gas chromotograpy and were $C_2H_2$, $C_2H_4$, HBr, $C_2H_5Br$, and $CH_3CHBr_2$. The neat primary processes at both wavelengthes were observed by blocking the secondary processes adding the radical scavengers, i.e., NO, $H_2S$, and HBr, and could be described by:
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Product quantum yield ratios, i.e., $\Phi_1/\Phi_2/\Phi_3$, for these processes at two wavelengthes were found to be 0.39/0.23/0.42 and 0.39/0.40/0.21 at 184.9 and 163.4nm, respectively.
본 연구는 기체크로마토그라피를 이용한 역이차동위원소 측정 방법과 비닐브로마이드의 광반응에 수반되는 분석방법에 관한 연구이다.
Part A 에서는 크로마토그램상의 겹친 피크를 성분 피크들로 분리할 수있는 기존의 방법보다 간단하고 진보된 방법을 제안하였다. 이 방법에서는 겹친 크로마토그램이 Exponentially Modified Gaussian (EMG) 함수의 합으로 가정된다. 이함수를 미분 크로마토그램을 이용하여 간단히 하였고, 초기치를 얻는 새로운 방법이 제시되었다. 컴퓨터를 이용한 모의 실험 결과 이 방법은 마이크로컴퓨터에 실용화 될 수 있음을 보였다. 이 방법의 타당성을 실험에서 얻은 피크에 적용시킨 결과로서 검토한 상대오차 1.6%이내, 표준분포 2.2%이내로 실험에서 얻은 크로마토그램을 재현시킬 수 있었다.
Part B 에서는 Rh(I)-$C_2H_4$ 와 Rh(I)-$C_2H_3D$ 사이이 역이차 동위원소 효과를 dicarbonyl-rhodium(I)-3-trifluroacetyl-1R-camphorate (RHC) 를 squalane에 녹인 용액을 고정상으로 사용한 분리관을 만들어서 측정하였으며, 또한 착화물의 진동수로써 표현된 분배함수를 사용하여서도 구할 수 있었다. 두 값사이의 신뢰할만한 일치를 보여주었다. 측정에서 구한 열역학적인 동위원소 효과는 엔탈피차 이값으로는 - 496 ± 12 J $mol^{-1}$ 엔트로피차이값으로는 - 0.975 ± 0.017 J $mol^{-1}K^{-1}$ 이었다. RHC-$C_2H_4$ 착화물을 적외선 분광법으로 조사한 결과로 부터 착화-기체크로마토그라피의 분리성능을 고정상 착화물과 에틸렌 결합시 발생하는 에틸렌-재혼성도로써 추정할 수 있다는 것을 제시하였다.
