首页化学分析化学仪器分析 12 (双语) 第二章 气相色谱法.ppt

12 (双语) 第二章 气相色谱法.ppt

页数:105页文件大小:1.41 MB来源: 仪器分析ppt课件

本课件以英文讲解气相色谱分析,涵盖色谱图与保留值术语、理论塔板数与塔板高度、分辨率计算,以及分离度与柱长、容量因子和选择性的定量关系。

Gas Chromatography slide, (GC)§2-1SummaryChromatographic separation
Mobile phase & Stationary讲解,phase(流动相与固定相):Chromatogra
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第1页:Gas Chromatography

Chapter 2 Gas Chromatography(GC)§2-1Summary

Chromatographic separation technique(色谱分离):A separation technique based on partition of 2 or more substances in mixture in two phases(色谱法、色层法、层析法,chromatographer)

Chromatographic analysis(色谱分析):Chromatographic separation applied on analytical chemistry Advantages:High separation efficiency, high detect ion efficiency, fast analyticalvelocityGC

第2页:Mobile phase & Stationary

Mobile phase & Stationary phase(流动相与固定相):Chromatographic separation involving partition of different species in mixture in two phases, amongwhich one phase (solid or liquid) does not move(stationary phase) , the other phase (gas or liquid) takesthe sample mixture to pass through the stationary phase packed in the column(mobile phase)Separations are affected due to the differences of substances’ affinities for mobile phase and stationaryphase(分离原理).GC

第3页:

第4页:Gas supply Flow

Gas supply Flow controller Oven Column To waste Detect or Flow meter(In one of these positions)Injection system Amplifier Integrator RecorderGC

第5页:皂膜流量计转字流量计调整仪

皂膜流量计转字流量计调整仪,标准仪Setup of Gas ChromatographGC

第6页:inert

inert gases wothoutinteraction with analytes or stationary phase管状的Thermal conductivity detect or Electron capture detect or, IR, FPD Flame photometric detect or Hydrogen flame ionization detect or

第7页:Chromatogram of

Chromatogram of xylene isomers on polar columnGC

第8页:Chromatogram of(续)

Y

第9页:GC0124Peak width at half

GC0124Peak width at half height Peak width at peak base Adjusted retention time Rotention time Dead time Air peak0.607h1/2h2sY1/2Yt'RtRtMInjectiont Response signal Chromatogram Time(arbitrary units)

第10页:Nomenclature

Nomenclature of Chromatographic separation

Chromatographic Curve & Chromatogram The chart of output detect or response (concentration)versus time Theprotuberance in the curve is calledchromatographic peak如果进样量很小,浓度很低,在吸附等温线(气固吸附色谱)或分配等温线(气液分配色谱)的线性范围内,则色谱峰是对称的。

第11页:Baseline

Baseline(基线)Chromatographic curve under theexperimental operation conditions, no components of materials flow out after the column(在实验操作条件下,色谱柱后没有样品组分流出时的流出曲线称为基线,反映检测器系统噪声(No ise)随时间的变化情况。稳定的基线应该是一条水平直线。)Nomenclature of Chromatographic separation

Baseline drift(基线漂移)refer to基线随时间定向的缓慢变化

Peak height refer to Verticaldistance from the vertexof chromatographic peak to baseline色谱峰顶点与基线之间的垂直距离,以(h)表示。

第12页:Nomenclature

Nomenclature of Chromatographic separation

Chromatogram and chromatographic peak

Baseline(a)

Peak height(h)信号进样空气峰色谱峰ha色谱流出曲线

第13页:Retentionvalue

Retentionvalue表示试样中各组分在色谱柱中滞留时间的数值。通常用时间或用将组分带出色谱柱所需载气的体积来表示。

Rely on component partition on two phases (or absorption)

Thermodynamic controlled (Properties of stationary phase & operation conditions)

Qualitative Base Nomenclature of Chromatographic separation

Dead Time tM不被固定相吸附或溶解的物质(如空气,甲烷等)进入色谱柱时,从进样到出现峰极大值(浓度)所需的时间称为死时间,它正比于色谱柱的空隙体积。见图

第14页:Rotention time tRThe time

Rotention time tRThe time at which the maximum of the peak appearsafter sample injection见图Nomenclature of Chromatographic separation因为这种物质不被固定相吸附或溶解,故其流动速度将与流动相流动速度相近。测定流动相平均线速ū时,可用柱长L与tM的比值计算,即ū = L/t

第15页:Nomenclature

Nomenclature of Chromatographic separation

Adjusted rotention time(tR´)The difference between the rotention time and dead time某组分的保留时间扣除死时间后,称为该组分的调整保留时间,即t R´= tR−tM•Moretimethecomponentspendsduetodissolutionin(or adsorption on)thestationaryphasethaninertcomponentswithoutinteraction.保留时间是色谱法定性的基本依据,但同一组分的保留时间常受到流动相流速的影响,因此色谱工作者有时用保留体积来表示保留值。

第16页:Dead VolumeVM

Dead VolumeVM指色谱柱在填充后,柱管内固定相颗粒间所剩留的空间、色谱仪中管路和连接头间的空间以及检测器的空间的总和。当后两相很小可忽略不计时,死体积可由死时间与色谱柱出口的载气流速F0(cm3·min-1)计算。VM= tMF0式中F0为扣除饱和水蒸气压并经温度校正的流速。•仅适用于气相色谱,不适用于液相色谱Nomenclature of Chromatographic separation

第17页:Rotention volumeVR

Rotention volumeVR指从进样开始到被测组分在柱后出现浓度极大点时所通过的流动相的体积。保留时间与保留体积关系:VR= tRF0= tMF0Nomenclature of Chromatographic separationVR,VR’ do not dep end on velocity of the carrier gas.

Adjusted rotention volumeVR′某组分的保留体积扣除死体积后,称为该组分的调整保留体积。VR′= VR−VM= tR′F0

第18页:The ratio of adjusted

The ratio of adjusted rotention value of the secondcomponent to that of the first componentr21= tR(2)′/ tR(1)´= VR(2)′/ VR(1)′≈tR(2)/ tR(1)≈VR(2)/ VR(1)由于相对保留值只与柱温及固定相性质有关,而与柱径、柱长、填充情况及流动相流速无关,因此,它在色谱法中,特别是在气相色谱法中,广泛用作定性的依据。Nomenclature of Chromatographic separation

The higher r21, the bigger difference between the adjusted rotention values of adjacent components , the better theseparation. When r21=1, the two components can not separateat all.

Relative rotention valuer21

第19页:在定性分析中

在定性分析中,通常固定一个色谱峰作为标准(s),然后再求其它峰(i)对这个峰的相对保留值,此时可用符号表示,即α= tR′(i)/ tR′(s)式中t R′(i)为后出峰的调整保留时间,所以总是大于1的。相对保留值往往可作为衡量固定相选择性的指标,又称选择因子。Nomenclature of Chromatographic separation

Peak width(区域宽度)色谱峰的区域宽度是色谱流出曲线的重要参数之一,用于衡量柱效率及反映色谱操作条件的动力学因素。表示色谱峰区域宽度通常有三种方法。

第20页:Standard

Standard deviationσ Half–widthofchromatographicpeakat0.607timespeakheight(0.607倍峰高处色谱峰宽的一半)Nomenclature of Chromatographic separation Due to easiness to measure, Y1/2is always used to denote peak width.

Peak width at half-height(半峰宽度、半峰宽、区域宽度)Y1/2即峰高一半处对应的峰宽。它与标准偏差的关系为Y1/2=2sSQR(2ln2)=2.354σ

Peak width at peak base(峰底宽度)Y即色谱峰两侧拐点上的切线在基线上的截距。它与标准偏差的关系是Y= 4σ

第21页:从色谱流出曲线中

从色谱流出曲线中,可以得到许多重要信息
Nomenclature of Chromatographic separation

Judge the number of the components included mixture based on the number of peaks

Qualitative analysis based on the rotention value ofchromatographic peak

Quantitative analysis based on are as or heights ofchromatographic peaks

Rotention value and peak width of chromatographic peaks is the basic to evaluate separation efficiency ofchromatographic column

色谱峰两峰间的距离,是评价固定相(或流动相)选择是否合适的依据。

第22页:Theoretical foundation

§2.2Theoretical foundation of gas chromatographic analysis2.2.1Gas solid or Gas liquid chromatography Capillary column(毛细管柱):The column has internal diameter of less than one mm, and inner wall of the column is usually coated with film of stationary liquid Chromatographiccolumn Packed column(填充柱):Packed stationary usually madefrom metal materials (copper or stainless steel) or glass, witha height of 0.5-10m and in side diameter of 2-6mm. U-shape or screwy(螺旋形)Stationary phase Gas-solid chromatography(气-固色谱):porous solid materials or adsorptive particles with higher surface area Mechanism:Adsorption & Elution (desorption)Gas-liquid chromatography(气-液色谱):Chemical inert solid particles(担体, support)coated with film of organicchemical of high-boiling point(Stationary liquid,固定液)Mechanism:Dissolution & volatilization

第23页:Theoretical foundation

§2.2Theoretical foundation of gas chromatographic analysis Partition Coefficient(K):Concentration ratio of the component in stationary phase and mobile phase when the partition processarrives at equilibrium under given temperature.K =Concentration of the component in stationary phase Concentration of the component in mobile phase=cS/cMGas chromatographic analysis based on the difference of thepartition coefficients of different substances Partition Process:Adsorption, elution, and dissolution,volatilization process of the substances between stationaryphase and mobile phase.

第24页:Theoretical foundation

§2.2Theoretical foundation of gas chromatographic analysis Partition ratio (capacity fact or, capacity ratio,k):Mass ratio of the component in two phases when partition processarrives at equilibrium under given temperature and pressurek = mS/ mMmSrefers to mass of the component distributed in stationaryphase, mSmass of the component distributed in mobile phase Relationship between and KK = cS/cM= (mS/VS) / (mM/ VM) =k VM/ VS= kb

第25页:VMrefers to mobile phase

VMrefers to mobile phase volume in column, that is,柱内固定相颗粒间的空隙(lacuna)体积。VS Stationary phase volume in column (在气-液色谱中为固定液体积,气-固色谱中为吸附剂的表面容量。Phase ratio(相比,b):VM/ VS,反映各种色谱柱柱型及其结构特征Packing column: 6-35, Capillary column: 50-1500

第26页:Stationary liquid

Stationary liquid Capillary wall Stationaryphase

第27页:Relationship of Kandk

Relationship of Kandk

refers to concentration ratio and mass ratio and depends on thermodynamic properties of the components and stationary phase, Tc(柱温),Pc(柱压)

Konly relys on properties of the component and doublephases, but not phase ratio. Butkrelys on not only properties of the component and double phases, but also phase ratio( amount of stationary phase)

With given chromatographic system, separation of the components is determined by relative amount of the components in both phases, but not relative concentration.The biggerkvalue, the longer rotention time, the easierseparation.k=0 corresponds to dead timet M.

第28页:Ratio of the velocity

Ratio of the velocity of carrier gas and the component in column:Rs= uS/u = = mM/ (mS+ mM) =1/(1+mS/ mM)= 1/(1+k)Whereurefers to velocity of carrier gas in column in unit ofcm.s-1,uvelocityof the component in column,wmassfraction.

Retardation fact or(滞留因子, Rs):

第29页:Defining as column length

Defining as column length, following formula are vivid:tR= / uStR= /uS= tMu /uS= tMu / uS= tM(1+k)k = (tR-tM) / tM= t’R/ tMtM= / uAbove equation can be employed to evaluatekvalue.

第30页:2.1Basic theory

  • 2.1Basic theory of chromatographic separation

Partition of different components in double phases Depending on partition coefficient, molecular structure and properties of the components, stationary phase, mobile phase.Characterized by rotention value (rotention time or rotention volume), thermodynamic controlled.

Movement of different components in column Depending on mass transfer(传质) resistance of different components in stationary phase and mobile phase.Characterized by peak width at half-height, kinetic controlled

第31页:Theories Two

Theories Two approaches can be taken to explain the separation process Plate theory–proposed in 1941 by Martin and Synge.Based on an analogy with distillation and counter currentextraction Rate theory–accounts for the dynamics of separation–1956, J. J. Van Deemter.Each has advantages and limit at ions.

第32页:Plate theory

Plate theory(塔板理论)借用传统的蒸馏过程处理色谱过程将色谱柱比作一个分馏塔,色谱柱由许多假想的塔板组成(即将色谱柱分成许多各小段),在每一个塔板内,一部分空间被涂在担体上的液相占据,另一部分空间则充满气相(载气),载气占据空间称为板体积DV.当欲分离的组分随载气进入色谱柱后,就在两相间进行分配。由于流动相在不停地移动,组分就在这些塔板间隔的气液两相间不断地达到分配平衡。

第33页:Plate theory

Plate theory assumes:

在一小段间隔(塔板)内,气相平均组成与液相平均组成能很快达到分配平衡。达到分配平衡的一小段柱长称为理论塔板高度H(Height equivalent to theoretical plate)

载气进入色谱柱,不是连续的,而是脉动式的,每次进气为一个板体积

试样开始时都加在第0号塔板上,且试样沿色谱柱方向的扩散(纵向扩散)可忽略不计

分配系数在各塔板上是常数

第34页:Assuming the column

Assuming the column consists of 5 plates, n=5 (number of theoretical plates), is defined as number of plate, r= 0,1, 2, …, n-1. Withm=1,k=1,w=1/2, when carrier gas of one more plate volume enters the column pulsantly, partition in each plate is shown as follows:Mass in mobilephase Mass in stationaryphase原塔板1固定相中组分的质量(0.125+0.125=0.25)与随载气带入的原塔板0流动相中组分质量(0.125)重新分配:(0.25+0.125)/2=0.188

第35页:Partition table of

Partition table of the component in any plate in columnwithn=5,k=1 andw=1/2Total amount of the solute in plate

第36页:Chromatogram of

Chromatogram of the component in column with n=5, is number of plate volume of carrier gas

Peak asymmetry since is too small

Concentration maximum at N= 8-9

Peak symmetry near normal distribution when > 50

n=103~ 106for gas chromatography

第37页:When number

When number of theoretical plates is big enough, chromatogramapproaches normal distribution curve, following relationship between concentration Cand timet is obtained:Where C0is injection concentration(进样浓度),Cconcentration at outlet(出口)of the column at timet流出曲线方程式

第38页:Relationship of to peak

Relationship of to peak width:Where Lis length of chromatographic column,tR,Y1/2,Yinthe same units,ntheoretical plate number,Htheoreticalplate height.

第39页:为了扣除死时间或死体积的影响

为了扣除死时间或死体积的影响,实际工作中常用有效塔板数(Effective plate number)和有效塔板高度(Effective plate height)作为柱效能指标:n=1+kk2•n有效

第40页:色谱柱的柱效能还与物质的性质有关

色谱柱的柱效能还与物质的性质有关,同一色谱柱的柱性能对不同物质是不同的。

色谱柱的理论塔板数越大,表示组分在色谱柱中达到分配平衡的次数越多,固定相的作用越显著,因而对分离越有利。但不能预言并确定各组分是否有被分离的可能,因为分离的可能性决定于试样混合物在固定相中分配系数的差别,而不决定于分配次数的多少。

n有效不能作为有无实现分离可能的依据,而只是在一定条件下柱分离能力发挥程度的标志。

塔板理论没有考虑动力学因素的影响,因而不能解决塔板高度受什么因素影响以及流速对理论塔板数的影响等问题。

第41页:

第42页:色谱柱的柱效能还与物质的性质有关(续)

(扩散)

第43页:Rate theory

Rate theory of chromatography It is based on Gaussian distribution similar tothat of plate theory He was attempting to account for the dynamics of the separation process.

第44页:H = + +CuBu

23H = + +CuBu0.01k2dp2(1+k)2Dgu+(填充的不均匀性)(弯曲因子)(组分在载气流中的分子扩散系数)(固定相的液膜厚度)

第45页:H = + +CuBu(续)

(涡流扩散项)(分子扩散项)(液相传质过程)0.01k2dp2(1+k)2Dgu Gas term(气相传质过程)

第46页:H = + +CuBu(续)

(涡流扩散项)(分子扩散项)(传质项)

第47页:涡流扩散项

涡流扩散项(vortex diffusion term)

由于填充物颗粒的阻碍作用,当气体通过时,会不断改变流动方向,使样品组分在气相中形成类似“涡流”的流动,引起色谱峰的扩张。涡流扩散项的大小与填充物的平均颗粒直径dp(单位未cm)大小及填充的不均匀性有关,而与载气性质,线速度和组分无关。

空心毛细管柱,涡流扩散项A为零。

使用细粒度和粒度分布均匀的颗粒作为担体,且填充均匀,可以减少涡流扩散,提高柱效能。

第48页:返回

返回

第49页:g与填充物有关

分子扩散项B/u(纵向扩散项)(Longitudinal diffusion term)试样组分被载气带入色谱柱后,以“塞子”的形式存在于柱内很小一端空间中,在“塞子”的前后(纵向)存在着浓差而形成浓度梯度,使运动着的分子产生纵向扩散。纵向扩散项的大小B为:B=2g Dgg为弯曲因子,表示因载体填充在柱内而引起气体扩散路径弯曲的因素。Dg为组分在气相中的扩散系数(cm2.s-1)B的影响因素:

g与填充物有关
由于固定相颗粒的存在,使分子不能自由扩散,从而使扩散程度降低。
空心毛细管柱
没有填充物的阻碍,扩散程度最大,g= 1
填充柱
由于填充物的阻碍,扩散路径弯曲,扩散程度降低,g<1.对于硅藻土担体,g= 0.5 ~ 0.7.

第50页:Dg与组分及载气的性质有关

纵向扩散项与组分在柱内的保留时间有关,保留时间越长(相当于载气流速越小),分子扩散项对色谱峰扩张的影响越显著。

分子扩散项与组分在载气流中的分子扩散系数Dg成正比。

Dg与组分及载气的性质有关
相对分子质量越大,Dg越小Dg与载气密度的平方根或载气相对分子质量的平方根成反比。Dg也随柱温的升高而增加,但与柱压成反比。

第51页:返回

返回

第52页:传质项C

传质项C (Resistance to mass transfer)包括气相传质阻力系数Cg和液相传质阻力系数Cl

第53页:气相传质过程

气相传质过程
Cg=0.01k2•dp2(1+k)2•Dg上式中k为容量因子。dp为填充物颗粒的平均直径。Cg∝dp2Cg∝1/Dg试样组分从气相移动到固定相表面的过程,在该过程中,试样组分将在两相间进行质量交换,即浓度分配。如气相传质过程速度慢,表示气相传质阻力大,便会引起色谱峰扩张。对于填充柱:对于填充柱,固定相含量较高,在中等线速时,Cg数值较小,通常可以忽略。

第54页:液相传质过程试样组分从固定相

液相传质过程试样组分从固定相的气液界面移动到液相内部,并发生质量交换,达到分配平衡,然后再返回气液界面的过程。在液相传质过程中,气相中的组分的其它分子仍然随载气不断地向柱口运动,从而造成峰形的扩张。component molecule Stationary liquidsupport液相传质阻力系数ClCl=2k df23(1+k)2Dldfrefer to thickness of liquid member of stationary phase Dldiffusion coefficient of the component in liquid phase

第55页:

第56页:Selection

§2-3 Selection and optimization of chromatographicseparation conditions

分离度(resolution)Whether mixture can be separated or not depends on the difference of interaction (partition coefficient)between stationaryphase and the various component molecules in the mixture andtheoperation conditions

Selecting appropriate stationary(possible separation,有分离可能性)

Selecting optimal operation condition(practical separation,实现可能性)完全分离的依据

Enough big distance between chromatographic peaks of two components

Enough thin peaks(见图)

第57页:

第58页:The ratio of

The ratio of the difference of chromatographic rotention values of two adjacent components and half of sum of peakwidths at peak base of two components(相邻两组分色谱峰保留值之差与两组分色谱峰峰底宽度总和之半的比值。分离度可以用来作为衡量色谱峰分离效能的指标。

R越大,表明两组分分离效果越好

保留值之差取决于固定液的热力学性质

色谱峰宽窄反映色谱过程动力学因素,柱效能高低对于峰形对称且满足正态分布的色谱峰:R=1,分离程度为98%;R=1.5,分离程度可达99.7%.R=1.5,可认为色谱峰已完全分开。分离度R:

第59页:当两组分色谱峰分离较差

当两组分色谱峰分离较差,峰底宽度难以测量时,可用半峰宽度代替峰底宽度:Basic equations to chromatographic separation(色谱分离基本方程式)对于多组分混合物,在选择固定相及实验操作条件时,主要考虑难分离物质对。由于其保留值差别很小,故可以认为Y1=Y2=Y,k1= k2=k,eq(2-18)可以变为:1n1/21Y 4 tR=

第60页:Base on above

Base on above hypothesis, basic equation for chromatographicseparation is defined as follows:14n1/2a-1ak1+k R=a为选择因子(*)或:R =14n有效1/2a-1a(**)

分离度的影响因素

第61页:与柱效的关系

与柱效的关系(柱效因子)R∝ n1/2增加柱长减小塔板高度限制:L过长,保留时间延长,分析时间延长,色谱峰扩展。使用性能优良的色谱柱,并选择最佳分离条件

与容量因子的关系k值增大,有利于分离,但k> 10时,对R的增加不明显,也会显著增加分析时间k的最佳范围:1 ~ 10

第62页:与柱选择性的关系a越大

与柱选择性的关系a越大,柱选择性越好,分离效果越好。如果两个相邻峰的选择因子足够大,则即使色谱柱的理论塔板数较小,也可以实现分离。

分离度、柱效、柱选择性的关系通过上式可以计算相关指标的值L =16R2•H有效aa-12= n有效•H有效

第63页:与柱选择性的关系a越大(续)

例
设有一对物质,其a=1.15,要求在某填充柱上得到完全分离,试计算至少需要多长的色谱柱?解:要实现完全分离,R≈1.5,故所需有效理论塔板数为:使用普通色谱柱,一般有效理论塔板高度为0.1cm,故所需柱长应为:

第64页:Selection of separation

Selection of separation conditions(分离操作条件的选择)

Selection of carrier gas and its flow rate

Selection of column temperature(自学)

Properties and amount of mixed liquid(自学)

Properties and size of supports(自学)

Injection time and injection amount(自学)

第65页:Selection of carrier gas

Selection of carrier gas and its flow rate According to Van Deemter equation:Following equation can be obtained by differentiating above equation:实际工作中,为了缩短分析时间,常使流速稍高与最佳流速。and

第66页:Combining above equation

Combining above equation and Van Deemter当流速较小时,H≈B/u,分子扩散项(B项)就成为色谱峰扩张的主要因素,此时应采用分子量较大的载气(N2、Ar),使组分在载气中有较小的扩散系数。而当流速较大队H≈Cu,传质项(C项)为控制因素,宜采用低分子量的载气(H2、He),此时组分在载气中有较大的扩散系数,可减小气相传质阻力,提高柱效。选择载气时还应考虑对不同检测器的适应性。对于填充柱,N2的最佳实用线速为10~12cm/s, H2为15~ 20cm/s,通常载气的流速习惯上用柱前的体积流速(mL/min)来表示,也可通过皂膜流量计在柱后进行测定。若色谱柱内径为3mm,N2的流通一般为40~60mL/min,H2的流速为60~90 mL/min。

第67页:Selection of column

Selection of column temperature(自学)Under stand how to select column temperature

Properties and amount of stationary liquid(自学)What influence does stationary liquid have, How to select?Requirement for mixed liquids, separation characterization

Properties and size of supports(自学)Definition of support, requirement for support, how to select it?

Injection time and injection amount(自学)How do they affect peak shape? How to select them?

第68页:Detectors of GC

§2-5 Detectors of GC(Concentration sensitive detect or & mass flow rate sensitive detect or)

第69页:Thermal conductivity

Thermal conductivity detect or(热导池检测器,TCD)Self-study & Exam:热导池的构造,工作原理及影响检测灵敏度的因素。

第70页:Hydrogen flame ionization

Hydrogen flame ionization detect or(氢火焰离子化检测器,FID)氢火焰电离化检测器,简称氢焰检测器。对大多数有机化合物有很高的灵敏度,一般比热导池检测器的灵敏度高几个数量级,能检测至ppb级(10-12g.s-1)的痕量物质,故适宜于痕量有机物的分析。结构简单,灵敏度高,响应快,稳定性好,线形范围宽(10-6).Self-study & Exam:结构、作用原理、操作条件

第71页:Electron capture detect

Electron capture detect or(电子俘获检测器,ECD)ECD

Flame photometric detect or(火焰光度检测器,FPD)FPD is highly sensitive and highly selective to the compoundscontainingsulphur,phosphor,etc.检测器

第72页:检测器的性能指标Self-study &

检测器的性能指标Self-study & Exam检测器的灵敏度、检出限,最小检出量、响应时间、线形范围等的概念,物理意义,计算公式等。

第73页:Qualitative analytical

§2-6Qualitative analytical methods for GC

Qualitative analysis based on chromatographic rotention value

直接根据色谱保留值进行定性各种物质在一定的色谱条件下(固定相、操作条件)均有确定的保留值,可以作为定性指标。适合于已知混合物及已确定存在范围或类型的化合物的鉴定对于完全未知的化合物鉴定,可靠性较差。方法的可靠性与色谱柱的分离效率(柱效)有密切关系常采用仅与柱温有关,而与操作条件(柱长、固定液含量、载气流速等)无关,重现性较好的相对保留值r21作为定性指标。

第74页:与文献值比较与标准样对照混合进样

与文献值比较与标准样对照混合进样:将标准样与未知物混合进样,通过观察是否有新峰出现,或未知峰上是否出现分叉等现象,判断未知物与标准样是否属同一物质。多柱法:通过多根不同性质的色谱柱分离实验,确定标准样与未知样是否属同一物质。不同物质在同一根色谱柱上可能具有相同的保留值。保留指数法(rotention index, Kovats index)Seen in next page

第75页:保留指数I

保留指数I
用两个紧靠近待测物质的标准物(一般选用两个相邻的正构烷烃)标定被测物质,并使用均一标度(即不用对数),用下式定义:I = 100lg Xi–lgXZlgXZ+1–lg XZ+ ZX为保留值(tR’, VR’,或相应的记录纸距离),下脚标i为被测物质,Z, Z+1为正构烷烃的碳原子数,XZ< Xi< XZ+1,IZ= Z×100

第76页:EXAMPLE Figure Sketch map

EXAMPLE Figure Sketch map for determinationof rotention index From the right figure, following data can be gotten = 7n-heptane:Butyl ester acetate:n-octane:

第77页:GC-MS

GC-MS,GC-IR,GC-chemical analysisITCABX1•••X2

第78页:Quantitative analysis

§2-7 Quantitative analysis of GC Under given chromatographic conditions, mass( or concentration in carrier gas) of analyte is directly proportional to response signal of the detect or (chromatographic peak area or height):mi= fi′• Aifi′refers to quantitative calibration fact or

第79页:Peak area measurements

Peak area measurements1.Peak area equals to product of peak height and peak width at half height =h• Y1/2上式计算得到的峰面积仅为实际面积的0.94倍,实际峰面积应为:A = 1.065h•Y1/2不过,在相对计算时,1.065常可以忽略特点:快速、简便,但不适合于不对称峰、窄峰、极弱峰。

第80页:Product of peak height

  • Product of peak height and peak width at peak base A≈ h×Y用本方法测得的峰面积约为真实面积的0.98倍。本方法适用于矮宽峰。3.Average peak width method(平均峰宽法)A = h×YY = (Y0.15+ Y0.85) /2本方法适用于不对称峰(asymmetrical)

第81页:Product of peak height

  • Product of peak height and rotention time Under given operation conditions, peak width at half-height of同系物is proportional to rotention time:Y1/2∝tRY1/2=btRA = h•Y1/2=bhtR相对计算时,常数b可以省略。特点:简便、快速,适用于狭窄峰,工厂控制分析。

第82页:积分仪

  • 积分仪(integral meter)Simple、convenient、fast、exact(precision ranges 0.2%~2%),and linear range wide

Quantitative calibration factormi= fi’ Aifi’ = mi/ Aifi’为绝对质量校正因子,表征单位面积所代表的物质质量,由仪器的灵敏度决定,一般不易准确测定。实际工作中常用相对校正因子。通常,同一检测器对不同物质的响应值不同,相同质量的不同物质往往具有不同的峰面积,因而不能直接用峰面积来计算被测物质含量。因此需要对仪器响应值进行校正。

第83页:Relative calibration fact

Relative calibration fact or Ratio of absolute calibration factors of the analyte and standard substance For TCD, benzene employed as standard For FID, n-heptane as standard Based on sought-out component’s units, following conceptsare employed:Mass calibration fact or Molar calibration fact or Volume calibration fact or

第84页:Mass calibration fact

  • Mass calibration fact or fmfm=f’i(m)f’s(m)Asmi Aims=Where I,s respectively refers to sought-out and standard substances2.Molar calibration fact or MfM=f’i(M)f’s(M)Asmi MsAimSMi== fm•MS Mi各物质的量以摩尔数计,MS,Mi分别表示被测物与标准物质的相对分子质量(摩尔质量)

第85页:

第86页:Volume calibration fact

  • Volume calibration fact or

第87页:Relative response value

  • Relative response value s’Ratio of response values (sensitivity) of the substance and standard sample s. When same unit is used, it is reciprocal of calibration fact or.s’ = 1 / f’s’, f’ only rely on properties of test sample, standard substance and type of detect or, but not operation condition, cloumn temperature,flow rate of carrier gas, property of stationary liquid.Measurement of calibration fact or Accurately weigh sought-out component and standard substance, after mixing, inject, analyze and determine corres-ponding peak area, and then calculate calibration factors using above equations.

第88页:Quantitative

Quantitative calculationmethods in common use•归一化法(Normalization method)•内标法(Internal standard method)•内标标准曲线法•(Internal standard curve method)•外标法(定量进样-标准曲线法)(External standard method)

第89页:归一化法

归一化法(Normalization method)When all of the components can flow out the column and and show chromatographic peaks, the contents of all of the components could be determined by normalization method.If the sample consists ofncomponents, and mass of each component is respectivelym1,m2,…, mn,sum of all components is 100%, then mass fractionwiof componentican be calculated by following expression:wi=mim×100%mim1+m2+…+mn×100%=AifiA1fi+ A2f2+ … + Anfn×100%mi Σmii×100%==

第90页:wi=mim×100%mim1+m2+…

wi=mim×100%mim1+m2+…+mn×100%=AifiA1fi+ A2f2+ … + Anfn×100%mi Σmii×100%==Iffiis mass calibration fact or, thenwistands for mass fraction,and iffiis molar calibration fact or, thenwimolar fraction or volume fraction (for gas sample).

第91页:Back

Back

第92页:内标法

内标法(Internal standard method)

第93页:所以

所以

第94页:特点

特点

适用于仅需测定部分组分或试样中其它组分不能全部出峰的情况

可消除由于操作条件变化而引起的误差,准确度高内标物质的选择:

每次分析均需准确测量,故不适合快速控制分析

第95页:内标标准曲线法

内标标准曲线法(Internal standard curve method)如果经常需要测定同一物质,可固定试样的称取量,并加入恒定量的内标物,此时fim S/fsm为一常数故:wi∝Ai/AS(or w)Figure Internal working graph适合于液体试样的常规分析Back

第96页:外标法

外标法(定量进样-标准曲线法,External standard method)所谓外标法就是应用欲测组分的纯物质来制作标准曲线。此时用欲测组分的纯物质加稀释剂(对液体样品用溶剂稀释、气体样品用载气或空气稀释)配成不同含量(%)标准溶液,取固定量标准溶液进样分析,从所得色谱图上测出响应讯号(峰面积或峰高等)、然后绘制响应汛号(纵坐标)对百分含量(横坐标)的标准曲线。分析试样时,取和制作标淮曲线时同样量的试样(固定量进样),测得该试样的响应讯号,由标准曲线即可查出其百分含量。Signalwi Aiwi

第97页:当被测试样中各组分浓度变化范围不大时

当被测试样中各组分浓度变化范围不大时,可不必绘制标准曲线,而用单点校正法。即配制一个和被测组分含量十分接近的标准溶液,定量进样,由被测组分和外标组分峰面积比或峰高比来求被测组分的含量:wi Aws As=wi= ws AiAs由于S为标样,wS和AS和均为已知故,令Ki=w S/AS,则:wi= Ki×AiKi为组分i的单位面积质量分数校正值。单点校正法(Single dot calibration method)

第98页:Capillary column gas

§2-8 Capillary column gas chromatography Self-study Problems:

Differences between capillary column GC and packing column GC

毛细管色谱柱分为哪几种类型?

毛细管柱有那些特点?

第99页:characteristics

§2-9characteristics and applications of GC

High analytical efficiency

High selectivity

High sensitivity

Simple operation

Wide applications

第100页:High analytical

High analytical efficiency & Selevtivity Based on partition of the components on double phasestime after time Packing column of 1~2m, n≈ 103Capillary column, ≈ 106For example, simultaneously separating and analyzing amixture including more than 100 components at one time using hollow capillary column.返回

第101页:High sensitivity For GC

High sensitivity For GC, mass sensitivity: 10-11~ 10-13g10-6~ 10-10(mass fraction) of impurities in ultra-pure gas,in monomer of polymer, and ultra-pure reagents can be detected.10-6~ 10-9(mass fraction) of pollutants in atmosphere can be directly detected.10-6~ 10-9(mass fraction) of halide, sulfide, phosphide infoods, water sample and so on.Back

第102页:Simple and fast operation

Simple and fast operation Several minutes to tens of minutes each test Easy to automation back

第103页:Wide applications

Wide applications Practicable for analyzing all kinds of gas samples,volatile ( or able to be transformed into volatile compound)liquid or solid samples Including:Organic, inorganic compounds with boiling point lowerthan 500℃ and molecular weight less than 400, and agood thermal stability.Splitting gas chromatography and reaction gas chromatography extend the application fields of GC

第104页:Exercises

Exercises

第105页:Back

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