從氣體工業的分析數據得知，目前產業界中最廣泛使用的氣體種類為氧、氮、氬及氦氣等，其主要應用於石化工業、環保氣體、實驗室、機械加工、航太工業、電子產業、食品加工、玻璃製造及氣體製造廠。標準氣體可以做為基本測量、儀器量測、儀器校正、生產品質監控等，具有標準量測的依據，氣體中微量的雜質含量一旦超過所要求的標準，就會對電子廠製程或其它工業製程產生嚴重的經濟損失及影響。因此準確量測高純度氣體中雜質含量是非常重要的，唯有準確量測氣體中雜質的含量才能確保氣體純度準確。
本論文有兩個研究主題一是利用重量法製備微量氣體混合物，以兩種基質氣體(氦氣及氧氣)分別與三種不同濃度的微量氣體(氬氣、氮氣和甲烷)混合配製；二是利用美國葛麥克公司(GOW-MAC)所生產的放電離子化偵測器(DID)，此種偵測器可同時檢測Ar、N2及CH4等微量氣體於氦氣及氧氣中的含量。
本研究利用氣相層析儀，以分子篩(molecular sieve；MS)管柱對微量氣體進行分析，連接放電離子化偵測器(DID)及氧氣捕捉器(Oxygen trap，model 75-900)輔助。由於MS管柱無法有效分離氧氣及氬氣，並且氦氣中通常含有微量的氧氣，所以有必要使用氧氣捕捉器事先去除氣體中的氧氣以利氬氣、氮氣及甲烷的定量分析。此方法可探討氣體中微量殘留氣體的含量，準確性與精密性高，實驗簡單，分析時間短，濃度線性關係R2可以到達0.999。

From the analytical data of gas industry it is known that at present the most widely use of gases are oxygen, nitrogen, argon and helium which are mainly used in petrochemical industry, environmental gases, laboratories, mechanical process, aerospace industry, electronics factory, food process, glass manufacture and gas plant. Standard gases can serve as a measuring tool for the basic measurement, the instrument measurement, instrument calibration and production quality control etc. If the impurities of gases are beyond the request standard, the gas users, which are electronic factories or other industries, will have serious economic loss and impact. It is thus clear that the purity measurement of gases is very important. Therefore, the precise methods of gas purity measurement can ensure the purity of gases.
There are two topics in this thesis. The first topic is to prepare gas with trace mixtures using the gravimetric method. There are two substrate gases (helium and oxygen) and three trace mixtures (argon, nitrogen and methane) were mixed. The second topic is using discharge ionization detector (DID) from GOW-MAC Corporation, UAS. This detector can simultaneously determine the contents of Ar, N2 and CH4 in helium and oxygen gases, respectively.
In this research, gas chromatography with molecular sieve column was used and connected with the discharge ionization detector (DID) and the oxygen trap (Oxygen trap, model 75-900). The molecular sieve column can not effectively separate oxygen as well as argon and usually helium contaminated with trace oxygen, therefore the oxygen trap is required to pre-remove oxygen in order to determine the contents of argon, nitrogen and methane in the gases. This method can analyze the residue of gases with high accuracy and precision, method simple, short run time, and R-square linear-relation of concentration beyond 0.999.

目錄:
中文摘要 ......................I
Abstract ......................II
誌謝 ......................III
目錄 ......................IV
圖目錄 ......................VIII
表目錄 ......................X
第一章 前言......................1
1.1 參考物質簡介......................3
1.2 參考物質的實際應用及其重要性......................4
1.3 標準氣體的定義 ......................5
1.4 標準氣體的作用 ......................5
1.5 標準氣體追溯體系......................6
1.6 微量氣體濃度分析方法之研究......................15
1.7 研究動機......................16
第二章 文獻回顧......................19
2.1 標準氣體的配製方法簡介......................19
2.2 氣體標準品的製備......................19
2.2.1 靜態稀釋法（static dilution method）..............21
2.2.2 動態稀釋法（dynamic dilution method）..............23
2.2.3 特殊性質標準氣體的配製..............26
2.3 儀器簡介..............27
2.3.1 質量流量計..............27
2.3.2 放電離子化偵測器原理..............29
2.3.3 氧氣捕捉器(Oxygen trap)..............33
第三章 試驗材料與研究方法..............35
3.1 混合氣體配製原理及計算公式..............35
3.1.1 混合氣體重量法配製原理..............35
3.1.2 混合氣體重量法配製配製原理..............36
3.1.3 混合氣體重量法配製計算公式..............36
3.1.4 低濃度混合氣標準品配製..............38
3.2 製備裝置與製備過程概要..............40
3.2.1氣瓶前處理裝置 ..............40
3.2.2 氣體充填裝置..............40
3.2.3 氣體秤重裝置..............41
3.2.4 配製過程..............42
3.3 實驗藥品..............46
3.4 實驗儀器及參數條件..............47
3.4.1 實驗儀器..............47
3.4.2 參數條件..............48
3.5 微量氣體濃度分析方法之研究..............48
3.5.1 氣體濃度分析步驟流程..............49
3.5.2 氣體分析取樣盤面系統..............50
3.5.3 儀器管路及閥切換路徑參數..............51
第四章 結果與討論..............53
4.1 微量混合氣體配製結果..............53
4.1.1 氦氣基質樣品配製結果..............53
4.1.2 氧氣基質樣品配製結果..............56
4.1.3 利用可追溯性標準氣體回收率驗證..............59
4.1.4 配製樣品於鋁瓶內濃度確認..............60
4.1.5 解析度計算及五種濃度分析圖譜建立.............. 66
4.2 氦氣基質配製濃度分析結果..............69
4.2.1 氦氣基質氣體樣品回歸曲線建立..............69
4.2.2 氦氣基質氣體樣品回收率試驗..............72
4.2.3 偵測極限(LOD)及回歸線性方程式..............73
4.3 氧氣基質配製濃度分析結果..............75
4.3.1 氧氣基質氣體樣品回歸曲線建立..............75
4.3.2 氧氣基質氣體樣品回收率試驗..............78
4.3.3 偵測極限(LOD)及回歸線性方程式..............79
第五章 結論..............82
第六章 參考文獻..............84

圖目錄:
圖一 荷蘭國家量測研究所(NMI)標準氣體參考圖........8
圖二 國家度量衡實驗室對氣體標準品的分類層級分類圖......11
圖三 標準物質校正階級........12
圖四 原級參考物質追溯鏈........14
圖五 不同標準氣體配製方法的分類........20
圖六 滲透管的結構示意圖........24
圖七 擴散法配製標準氣體之擴散瓶........25
圖八 MFC sensor構造圖........29
圖九 放電離子化偵測器構造圖 ........30
圖十 放電離子化偵測器波鋒面積/峰高比 ........31
圖十一 氧氣捕捉器(Oxygen trap)流程........34
圖十二 重量法配製裝置示意圖 ........40
圖十三 充填配製工作流程圖........43
圖十四 高壓充填系統示意圖........44
圖十五 氣體分析步驟流程圖........49
圖十六 氣體分析盤面系統........50
圖十七 儀器閥切換圖(Load Sample)........51
圖十八 儀器閥切換圖(Inject MS)........52
圖十九 購至SCOTT公司(Ar+N2+CH4)/He標準品圖譜........62
圖二十 樣品5ppm(Ar+N2+CH4)/He分析圖譜 ........63
圖二十一 購至SCOTT公司1ppm(Ar+N2+CH4)/O2標準品圖譜......64
圖二十二 樣品 5ppm(Ar+N2+CH4)/O2 分析圖譜........65
圖二十三 氧氣基質中五種濃度樣品成分確認........67
圖二十四 氦氣基質中五種濃度樣品成分確認........68
圖二十五 樣品5~50ppm Ar/He濃度檢量線........69
圖二十六 樣品5~50ppm N2/He濃度檢量線........70
圖二十七 樣品5~50ppm CH4/He濃度檢量線 ........70
圖二十八 氦氣基質氣體空白試驗........72
圖二十九 樣品5~50ppm Ar/O2濃度檢量線........75
圖三十 樣品5~50ppm N2/O2濃度檢量線........76
圖三十一 樣品5~50ppm CH4/O2濃度檢量線 ........76
圖三十二 氧氣基質氣體空白試驗........78

表目錄:
表一 分析儀器及條件........48
表二 氦氣基質中間氣體樣品理論配製重量........54
表三 氦氣基質中間氣體樣品實際配製重量........ 54
表四 中間氣體樣品稀釋五種低濃度氦氣基質樣品混合氣體.....55
表五 (Ar+N2+CH4)/He微量混合氣體實際配製濃度........56
表六 氧氣基質中間氣體樣品理論配製重量 ........57
表七 氧氣基質中間氣體樣品實際配製重量 ........57
表八 中間氣體樣品稀釋五種低濃度氧氣基質樣品混合氣體.....58
表九 (Ar+N2+CH4)/O2微量混合氣體實際配製濃度........59
表十 SCOTT公司標準氣體的濃度及標準偏差........61
表十一 兩種基質氣體滯留時間及解析度........66
表十二 氦氣基質氣體樣品平均面積及相對標準偏差........71
表十三 氦氣基質氣體樣品偵測極限及回歸線性方程式........73
表十四 氦氣基質氣體樣品回收率........74
表十五 氧氣基質氣體樣品平均面積及相對標準偏差........77
表十六 氧氣基質氣體樣品偵測極限及回歸線性方程式........79
表十七 氧氣基質氣體樣品回收率........80

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