粒子收取光譜解析儀器定理和組配
當某種元素被激發後,核外電子從基態E0激發到最接近基態的最低激發態E1叫共振激發。當其又回到E0時(shi)發(fa)出(chu)的(de)輻(fu)射(she)光(guang)線(xian)即(ji)為(wei)共(gong)振(zhen)線(xian)。而(er)基(ji)態(tai)原(yuan)子(zi)吸(xi)收(shou)共(gong)振(zhen)線(xian)輻(fu)射(she)也(ye)可(ke)以(yi)從(cong)基(ji)態(tai)上(shang)升(sheng)至(zhi)最(zui)低(di)激(ji)發(fa)態(tai),由(you)於(yu)各(ge)種(zhong)元(yuan)素(su)的(de)共(gong)振(zhen)線(xian)不(bu)相(xiang)同(tong),並(bing)具(ju)有(you)一(yi)定(ding)的(de)特(te)征(zheng)性(xing),所(suo)以(yi)原(yuan)子(zi)吸(xi)收(shou)僅(jin)能(neng)在(zai)同(tong)種(zhong)元(yuan)素(su)的(de)一(yi)定(ding)特(te)征(zheng)波(bo)長(chang)中(zhong)觀(guan)察(cha)到(dao),當(dang)光(guang)源(yuan)發(fa)射(she)的(de)某(mou)一(yi)特(te)征(zheng)波(bo)長(chang)的(de)光(guang)通(tong)過(guo)待(dai)測(ce)樣(yang)品(pin)的(de)原(yuan)子(zi)蒸(zheng)氣(qi)時(shi),原(yuan)子(zi)中(zhong)的(de)外(wai)層(ceng)電(dian)子(zi)將(jiang)選(xuan)擇(ze)性(xing)地(di)吸(xi)收(shou)其(qi)同(tong)種(zhong)元(yuan)素(su)所(suo)發(fa)射(she)的(de)特(te)征(zheng)譜(pu)線(xian),使(shi)光(guang)源(yuan)發(fa)出(chu)的(de)入(ru)射(she)光(guang)減(jian)弱(ruo),可(ke)以(yi)將(jiang)特(te)征(zheng)譜(pu)線(xian)因(yin)吸(xi)收(shou)而(er)減(jian)弱(ruo)的(de)程(cheng)度(du)用(yong)吸(xi)光(guang)度(du)A表示,A與被測樣品中的待測元素含量成正比;即(ji)基(ji)態(tai)原(yuan)子(zi)的(de)濃(nong)度(du)越(yue)大(da),吸(xi)收(shou)的(de)光(guang)量(liang)越(yue)多(duo),通(tong)過(guo)測(ce)定(ding)吸(xi)收(shou)的(de)光(guang)量(liang),就(jiu)可(ke)以(yi)求(qiu)出(chu)樣(yang)品(pin)中(zhong)待(dai)測(ce)的(de)金(jin)屬(shu)及(ji)類(lei)金(jin)屬(shu)物(wu)質(zhi)的(de)含(han)量(liang),對(dui)於(yu)大(da)多(duo)數(shu)金(jin)屬(shu)元(yuan)素(su)而(er)言(yan),共(gong)振(zhen)線(xian)是(shi)該(gai)元(yuan)素(su)所(suo)有(you)譜(pu)線(xian)中(zhong)最(zui)靈(ling)敏(min)的(de)譜(pu)線(xian),這(zhe)就(jiu)是(shi)原(yuan)子(zi)吸(xi)收(shou)光(guang)譜(pu)分(fen)析(xi)法(fa)的(de)原(yuan)理(li),也(ye)是(shi)該(gai)法(fa)之(zhi)所(suo)以(yi)有(you)較(jiao)好(hao)的(de)選(xuan)擇(ze)性(xing),可(ke)以(yi)測(ce)定(ding)微(wei)量(liang)元(yuan)素(su)的(de)根(gen)本(ben)原(yuan)因(yin)。原(yuan)子(zi)吸(xi)收(shou)光(guang)譜(pu)分(fen)析(xi)儀(yi)器(qi)原(yuan)子(zi)吸(xi)收(shou)光(guang)譜(pu)分(fen)析(xi)儀(yi)器(qi)的(de)原(yuan)理(li)是(shi)通(tong)過(guo)火(huo)焰(yan)、石(shi)墨(mo)爐(lu)等(deng)將(jiang)待(dai)測(ce)元(yuan)素(su)在(zai)高(gao)溫(wen)或(huo)是(shi)化(hua)學(xue)反(fan)應(ying)作(zuo)用(yong)下(xia)變(bian)成(cheng)原(yuan)子(zi)蒸(zheng)氣(qi),由(you)光(guang)源(yuan)燈(deng)輻(fu)射(she)出(chu)待(dai)測(ce)元(yuan)素(su)的(de)特(te)征(zheng)光(guang),在(zai)通(tong)過(guo)待(dai)測(ce)元(yuan)素(su)的(de)原(yuan)子(zi)蒸(zheng)氣(qi)時(shi)發(fa)生(sheng)光(guang)譜(pu)吸(xi)收(shou),透(tou)射(she)光(guang)的(de)強(qiang)度(du)與(yu)被(bei)測(ce)元(yuan)素(su)濃(nong)度(du)成(cheng)反(fan)比(bi),在(zai)儀(yi)器(qi)的(de)光(guang)路(lu)係(xi)統(tong)中(zhong),透(tou)射(she)光(guang)信(xin)號(hao)經(jing)光(guang)柵(zha)分(fen)光(guang),將(jiang)待(dai)測(ce)元(yuan)素(su)的(de)吸(xi)收(shou)線(xian)與(yu)其(qi)他(ta)譜(pu)線(xian)分(fen)開(kai)。經(jing)過(guo)光(guang)電(dian)轉(zhuan)換(huan)器(qi),將(jiang)光(guang)信(xin)號(hao)轉(zhuan)換(huan)成(cheng)電(dian)信(xin)號(hao),由(you)電(dian)路(lu)係(xi)統(tong)放(fang)大(da)、處理,再由CPU及外部的電腦分析、計算,最終在屏幕上顯示待測樣品中微量及超微量的多種金屬和類金屬元素的含量和濃度,由打印機根據用戶要求打印報告單。
常(chang)用(yong)的(de)光(guang)源(yuan)有(you)空(kong)心(xin)陰(yin)極(ji)燈(deng)及(ji)無(wu)極(ji)放(fang)電(dian)燈(deng)。空(kong)心(xin)陰(yin)極(ji)燈(deng)的(de)構(gou)造(zao),是(shi)由(you)待(dai)測(ce)元(yuan)素(su)材(cai)料(liao)製(zhi)成(cheng)圓(yuan)筒(tong)形(xing)空(kong)心(xin)陰(yin)極(ji),由(you)鎢(wu)材(cai)料(liao)製(zhi)成(cheng)棒(bang)型(xing)陽(yang)極(ji),兩(liang)電(dian)極(ji)密(mi)封(feng)在(zai)充(chong)有(you)惰(duo)性(xing)氣(qi)體(ti)、前端帶有英石窗的玻璃燈管中。在工作時,儀器的電源電路為燈的陰極和陽極之間加上200~500V的(de)電(dian)壓(ya),根(gen)據(ju)不(bu)同(tong)元(yuan)素(su)檢(jian)測(ce)要(yao)求(qiu),提(ti)供(gong)不(bu)同(tong)的(de)燈(deng)工(gong)作(zuo)電(dian)流(liu)。燈(deng)通(tong)電(dian)後(hou),陰(yin)極(ji)發(fa)出(chu)的(de)電(dian)子(zi)在(zai)電(dian)場(chang)作(zuo)用(yong)下(xia)加(jia)速(su),與(yu)惰(duo)性(xing)氣(qi)體(ti)碰(peng)撞(zhuang),使(shi)其(qi)電(dian)離(li),電(dian)離(li)後(hou)的(de)正(zheng)離(li)子(zi)向(xiang)陰(yin)極(ji)加(jia)速(su)運(yun)動(dong),轟(hong)擊(ji)陰(yin)極(ji)表(biao)麵(mian),使(shi)陰(yin)極(ji)材(cai)料(liao)的(de)原(yuan)子(zi)濺(jian)射(she)出(chu)來(lai)聚(ju)集(ji)在(zai)陰(yin)極(ji)附(fu)近(jin),電(dian)子(zi)不(bu)斷(duan)接(jie)受(shou)能(neng)量(liang),由(you)低(di)能(neng)級(ji)躍(yue)遷(qian)到(dao)高(gao)能(neng)級(ji),而(er)高(gao)能(neng)態(tai)是(shi)不(bu)穩(wen)定(ding)的(de),瞬(shun)間(jian)要(yao)從(cong)高(gao)能(neng)態(tai)返(fan)回(hui)到(dao)原(yuan)來(lai)的(de)基(ji)態(tai),同(tong)時(shi)發(fa)射(she)出(chu)與(yu)待(dai)測(ce)元(yuan)素(su)相(xiang)同(tong)的(de)特(te)征(zheng)光(guang)譜(pu),由(you)於(yu)許(xu)多(duo)元(yuan)素(su)的(de)光(guang)譜(pu)處(chu)於(yu)紫(zi)外(wai)區(qu),所(suo)以(yi)燈(deng)的(de)透(tou)光(guang)窗(chuang)須(xu)使(shi)用(yong)石(shi)英(ying)玻(bo)璃(li),燈(deng)的(de)供(gong)電(dian)一(yi)般(ban)采(cai)用(yong)脈(mai)衝(chong)電(dian)壓(ya),為(wei)使(shi)燈(deng)發(fa)光(guang)強(qiang)度(du)穩(wen)定(ding),供(gong)電(dian)電(dian)流(liu)采(cai)用(yong)穩(wen)流(liu)措(cuo)施(shi),要(yao)求(qiu)電(dian)流(liu)波(bo)動(dong)度(du)小(xiao)於(yu)0.1%。
wujifangdiandengyibanyongyuzhengqiyajiaogaodeyuansuhuohuahewudecedingshang,zhezhongdengshiyigeshiyingguan,guanneifangjinshuhaokejinshuhuahewubingchongyouyaqi。gongzuoshijiangdengzhiyugaopindianchangzhong,yaqijifa。suizheguanneiwendushenggao,jinshuhuahewuzhengfachulai,bingjinyibulijie、激發,從而輻射出金屬元素的共振線。主要用砷、硒、鎘、錫、guijinshudengyuansudeceding。yuanzihuaqiyuanzihuaqidezuoyongshitigongyidingdenengliang,shidaiceyangpinzhongdeyuansuyoulichuzhengqijitaiyuanzi,bingshiqijinruguangyuandefusheguangcheng,jinxingxishou。youyuyuanzixishouguangpufenxishijianlizaijitaiyuanzizhengqiduigongzhenxianxishoudejichushanglaifenxiyuansuhanliangdefangfa,suoyigezhongleixingyangpindeyuanzihuashifenxizhongzuiguanjiandewenti,cedingyuansudejieguoshifouzhunque,hendachengdushangqujueyuyangpindeyuanzihuazhuangtai。zhejiuyaoqiuyuanzihuaqijinkenengyougaodeyuanzihualv,bingqiewending、重現性好,幹擾少和裝備簡單,現在儀器最常用的有兩種原子化器,火焰原子化器和石墨爐。
(1)火焰原子化器是最常用的原子化器,包括2個部分:把(ba)樣(yang)品(pin)溶(rong)液(ye)變(bian)成(cheng)高(gao)度(du)分(fen)散(san)狀(zhuang)態(tai)的(de)霧(wu)化(hua)器(qi)和(he)燃(ran)燒(shao)頭(tou)。工(gong)作(zuo)時(shi),由(you)儀(yi)器(qi)外(wai)設(she)的(de)空(kong)壓(ya)機(ji)提(ti)供(gong)壓(ya)縮(suo)空(kong)氣(qi)作(zuo)為(wei)助(zhu)燃(ran)氣(qi)。由(you)管(guan)道(dao)進(jin)入(ru)霧(wu)化(hua)器(qi),並(bing)在(zai)出(chu)口(kou)處(chu)以(yi)高(gao)速(su)度(du)噴(pen)出(chu),會(hui)造(zao)成(cheng)局(ju)部(bu)負(fu)壓(ya),使(shi)得(de)樣(yang)品(pin)溶(rong)液(ye)在(zai)大(da)氣(qi)壓(ya)作(zuo)用(yong)沿(yan)進(jin)樣(yang)毛(mao)細(xi)管(guan)上(shang)升(sheng),隨(sui)壓(ya)縮(suo)空(kong)氣(qi)一(yi)同(tong)噴(pen)入(ru)霧(wu)室(shi)中(zhong)。樣(yang)品(pin)霧(wu)滴(di)、zhuranqiyuranqiyiqizaiwuhuaqizhongchongfenhunhehoujinruranshaoqi,jieranshaohuoyandereliang,shidaiceyuansuyuanzihua,changyongderanqiweiyique,yiqiwaijiegaochunyiqueqiguan,yiyiquezuoranqi。ranshaotouyiqijuncaiyongchangfengshi,younaigaowenhejincailiaozhicheng,butongxinghaodeyiqiqiranshaotoudefengchanghefengkuanbuyiyang,yibanyou10、7、5cm等幾種,縫寬在0.5mm左右。
(2)石墨爐:最常用的是管型高溫石墨爐,由於石墨是導體,當在石墨管兩端接上正負電極,通上十幾伏電壓和400 ̄500A之間的大電流時,石墨管會在2 ̄4s的短時間內,升到2000℃ ̄3000℃的高溫,將加入到石墨爐中的樣品蒸發→分解→原子化,石墨管的內徑通常在4 ̄6mm,長度在25 ̄50mm之間。為了防止石墨管和原子化的原子被氧化,儀器中的石墨管均封閉在一個保護氣室裏,加熱時,石墨管內外均通有惰氣氣體氬氣(Ar)。為了降低爐體對周圍的熱輻射,爐體外還通有冷卻水,保持原子化器的外邊在60℃以下。
石墨爐原子化器,原子化效率高,所需樣品量較少,檢測靈敏精密度高,使用石墨爐原子化時,樣品要經過幹燥→灰化→原子化→淨化4個過程。每個過程分別對應不同的溫度,由儀器控溫電路控製實施。(1)幹燥:是在等於或稍高於溶劑沸點的溫度下加熱數10s,將溶液烘幹,除去溶劑。(2)灰化:在低於原子化的溫度下加熱數秒鍾,將被測樣品中有機物盡可能除去,減少基體組分可能帶來的幹擾。(3)原子化:在被測元素的原子化溫度下加熱數秒鍾,同時儀器檢測係統記錄此時的吸光度值A。(4)淨化:檢測完畢,加高溫將石墨管內殘渣燒盡,開始下一次檢測,這4geguochengshijietishideshengwenchengxu,cedingbutongdeyuansushi,gejieduanshiyongdewenduheshijianbujinxiangtong,xianzaideyiqijunyouweijikongzhi,genjusuoceyuansuhuocaozuozheyuxianshedingdeshuzhizidongwancheng。中國糧油儀器網 http://98fo.cn/



