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x {Instructor: Prof. Wu YANG Office : Chemical Building 205 Office Tel: 0931-7971989(FAX) Email: yangw@nwnu.edu.cn&|jfPj 8 z  z @ 9  z l@ T,  9 X  C (ABannerT, Z  s *S M s Z  s *#    0?"0@NNN?N/g   0?"0@NNN?N@-  0?"0@NNN?N   0J?"0@NNN?N/3 8UV-VIS  0N?"0@NNN?Nz /  4GC  0R?"0@NNN?N#  6HPLC  0W?"0@NNN?N"  6FTIR  0Y?"0@NNN?N   JAES AAS MS  0[?"0@NNN?N G ; EMMISSION   0`?"0@NNN?N]D = ELECTROCHEM p  JA޽h ?e~"  33___PPT10i.0`lQ+D=' ~= @B +f 0 }u@((  ( ( 6Lä?"0@NNN?N  - c-INSTRUMENTAL ANALYSIS e-COURSE NOTE..,PP ( c $Ȥ?"0@NNN?NS Z s  F By WU YANG gB ( s *ff޽h ? 33___PPT10i.0pn+D=' ~= @B + 0  P$(  $ $ 0ڤ?"0@NNN?Np Q V TEXTBOOKS: (8Xz $ c $?"0@NNN?Nuw,$  0 %Instrumental Analysis Zhu Ming-hua Higher Education Press(3rd)(Textbook for 21th Century), Beijing, 2001(in Chinese)^x*>: \ $ c $H?"0@NNN?Nu ,$  0 % Modern Analytical Chemistry, David Harvey, McGraw-Hill, Inter. Ed., Singapore, 2000<\x Rp $ 0?"0@NNN?N. u,$  0 % Contemporary Instrumental Analysis, K.A.Rubinson, J.F. Rubinson, Science Press & Prentice Hall, Inc., Beijing, 2000(q_pSHr <x$^>$  : $ 63?"6@`NNN?N/]B $ s *޽h ? 33ia___PPT10A.0Uױ+d:52Dm' = @B D(' = @BA?%,( < +O%,( < +D{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*$%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*$D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*$D{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*$%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*$D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*$D{' =%(D#' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*$%(D' =+4 8?\CB#ppt_xBCB#ppt_xB*Y3>B ppt_x<*$D' =+4 8?dCB1+#ppt_h/2BCB#ppt_yB*Y3>B ppt_y<*$D' =%(D~' =%(D&' =4@BBBB%(D' =?B70, 0; .2, .5; .8, .5; 1, 0-g6B fade*<3<*$D' =0l9 BBBB*<3<*$)?++0+$0 ++0+$0 ++0+$0 + 0 H@` 0(  0 0 0 ?"0@NNN?NDx) NHOW to study this course$ 0 0!?"0@NNN?N36  8   0u `  0 0#?"0@NNN?N# ^%q`NhVRg zTzvcĉ_ Tyelv aINSyrp0TyRgelvT|T:S+R 000$,&  0 0x*?"0@NNN?NPp 6%EQRS%cf[uvR\O(u ZP0R^uNRS nSEu0  0 0.?"0@NNN?N  |,%OS}YXf[`NNT Y`N0MR`NvsQ|0  0 c $3?"0@NNN?N C  h%u[Xy^TX~_   0 Hx7?"6@ `NNN?NM >PP B 0 s *޽h ? 33  ___PPT10 .0<+D ' 9= @B D' = @BA?%,( < +O%,( < +D' =%(D' =%(Dn' =A@BB BB0B%(D' =1:B 0.5*3>%Bstyle.opacity= B PPT<*0D' =-6B image0BIE*v3=2Bopacity: 0.5 BIE<*0D' =%(D' =%(DF' =A@BBBB0B%(D' =/u8CC*Q3> Br<*0D' =%(D' =%(D3' =A@BBBB0B%(D' =?B70, 0; .2, .5; .8, .5; 1, 0-g6B fade*<3<*0D' =0l9 BBBB*<3<*0)?++0+00 ++0+00 ++0+00 +{ 0 p((    s *PP B  s *޽h ? 33___PPT10i.0Y<+D=' ~= @B +1  0   @(  @ @ 0Dq?"0@NNN?N  GChapter 1 PREFACE  @ 6h?"0@NNN?N{q%g Description of Validation Parameters Accuracy Closeness of agreement between the value obtained by the method and the true value. f%GGCSGC$ @ C xPPvd @?"6@ NNN?N= >PP   @ 6̋?"0@NNN?Nq% ,$ 0 oPrecision Expresses the closeness of agreement between a series of measurements obtained from multiple sampling. Precision is often expressed as the standard deviation or Relative standard deviation of replicate measurements (later on RSD). Note that a method can be precise, but not accurate (so all your measurements may be close together, but the result is wrong).Bp GCfGB @ s *޽h ? 33___PPT10.09C+ DO' ~= @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<* @%(+8+0+ @0 +  0 (  x  B?"0@NNN?NT,  HSpecificity The ability to measure the analyte in the presence of components which we expect to be present in the sample matrix. So if you are determining the concentration of Iron and Chromium in water by UV/Vis spectroscopy, if there are small amounts of Fluoride and Chloride in the sample, will that affect your measurement?6I =,'ue  B4?"0@NNN?N% T ,$ 0 Detection Limit The lowest amount of analyte in a sample that can be detected, but not necessarily quantitated. Usually the lowest limit is evaluated as the Signal-to-Noise ratio that is equivalent to 3 times the standard deviation of the noise ( S/N = 3s).6,%7 B  s *޽h ? 33___PPT10.FP@&I+'DO' ~= @B D ' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*%(+8+0+0 +O 0   1 (    BX?"0@NNN?Nj Quantitation Limit The lowest amount of analyte in a sample that can be quantitated with suitable precision and accuracy. Usually the Quantitation limit is evaluated as the Signal-to-Noise ratio that is equivalent to 10 times the standard deviation of the noise ( S/N = 10s).V{H  3   H?"0@NNN?N5G| ? Continued   H?"6@ `NNN?N >PP   B?"0@NNN?N`',L ,$ 0 'Linearity The range of concentrations of analyte for which the procedure provides test results that are in direct correlation to the amount of analyte in the sample.2 GG,)_r  BH?"0@NNN?N 'v,$ 0 Range The same as linearity, except the test results must also be accurate and precise (over the concentrations tested). Robustness (Ruggedness) Measure of an method s capacity to remain unaffected by small but deliberate variations in method parameters. zGCsGGmGCB  s *޽h ? 33\T___PPT104.0<+[udD' ~= @B DS' = @BA?%,( < +O%,( < +DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*%(+p+0+0 ++0+0 +O 0 f^(    H?"0@NNN?Nw  ? Continued $  H\?"0@NNN?N  6Analysis, Assay, Determination, Measurement, Identification These phrases are usually used to describe one process to determine the concentration of the analytes in a sampleJ-PPr   <?"0@NNN?N  Protocol, operation, method, procedure, measure, technique These phrases means a method to evaluate the concentration of the analytes in a sample:;V} *  S ~lPPvd @?"6@ NNN?N<j >PP B  s *޽h ? 33___PPT10i.0EѸ+D=' ~= @B +7  0 N F (    s *2  P xRgSf[ Sf[Rg0NhVRg(   c $7 j R%Analytical chemistry A subject to study chemical composition, structure and state of substances including chemical analysis and instrumental analysis. %Chemical analysis A method to determine chemical composition and content of the analytes in a sample based on chemical reaction and stoichiometric relation of teactants usually requiring chemical reagents, balance and glassware. % Instrumental analysis is an analytical method based on determination of physical and physical chemical properties which needs some complicated apparatus. %NhVRgvNu:NRgSf[&^egi}T'`vSS NhVRg/fRgSf[vSU\eT0\BGGCGGGGCGGPPG#P, %$  C xPPvd @?"6@ NNN?N<j >PP B  s *޽h ? 33___PPT10i.0Bc+D=' ~= @B +K  0 bZ(    s *P ` dCharacteristics of Instrumental Analyses NSf[Rgk  33G )   c $R v L%Higher sensitivity, detection limit down to lower level Y7hT(uϑ1uSf[RgvmL0mg~MNO0RNhVRgvmg0mL~ ufNO0TN_ϑmicro-)0uϑ(trace)Tuϑ(ultratrace)bRvKm[0 % Higher selectivity _YvNhVRgelSNǏ bbteKm[vagN OqQX[v~RKm[e vN NNur^pb0 % Simpler operation, faster assay & easy of automation % Poorer relative error Sf[RgN,S(uN8^ϑTؚ+TϑbRRg Qnx^ؚ ]\NCSRKNQ0YpeNhVRgv[]'Y N,:N5% N(uN8^ϑTؚ+TϑbRRg0 % More expensive apparatus$G8:G,G6GFG;    ,M3  H8?"6@ `NNN?NzF >PP B  s *޽h ? 33___PPT10i.0ac+D=' ~= @B + 0 f(    s *  Z  d8^ϑRg0JS_ϑT_ϑRg$ l  0A ? vqAY   H`?"6@ `NNN?N6M >PP B  s *޽h ? 33___PPT10i.0p+D=' ~= @B +)  0 -tp(  t8 I (tI t H?"0@NNN?NI \%Potentiometry(Half-cell potention) %Conductimetry (Conductance) %Voltammetry (Polarography,stripping Voltammetry,Current-voltage) %Coulometry (Charge) %Amperometry (current) PP PP PP2PP  PP  PP      @ ! #t! t H@?"0@NNN?N:! KElectrochemical analysisB t 6D?"0@NNN?N:<<l { I )t{ I,$D 0~ t <?"0@NNN?N{ I ~%Gas Chromatography %Liquid Chromatography &Partition in phases8@+EPPPP@ 0 "t0 t <?"0@NNN?N0 KChromatographic analysisB t 6D?"0@NNN?Nl P *tP,$D 0 t H?"0@NNN?Ng   %Emission spectra %Flame spectroscopy %Fluorescence %Phosphorescence &Emission of radiationJ]3PPl t H?"0@NNN?Nc  P%Spectrophotometry (UV,IR, Raman) %Atomic absorption spectroscopy %Nuclear magnetic Resonance Spectroscopy %Electro-spin Resonance Spectroscopy &Absorption of radiation&PPv t H8?"0@NNN?N C bb\l r^ml S\lI{ Refraction, Reflection of radiation&2 $ PP$T t Hx?"0@NNN?N m3  2Jm^lDisperse of radiation4   PPx t H?"0@NNN?N P NX-ray M\ 5uP[M\I{Diffraction of radiation4(   PP T t H?"0@NNN?N q$  @OP/c eIQ WNrI{Rotation of radiation&!   PP 2@ )  $t)  t H?"0@NNN?N   BOptical analysis@  )  !t ) B t 6D?"0@NNN?N  g B t 6D?"0@NNN?N) B t 6D?"0@NNN?N) ) B  t 6D?"0@NNN?NJ &t H?"0@NNN?Ne^ L,$ 0 f Mass spectra (Mass/charge ratio)*! PPl   +t ,$D 0  t H0?"0@NNN?NB  AThermo-analysis %t HD?"0@NNN?N(  @TG, DTA, DSC, B 't 6D?"0@NNN?NP -t H?"0@NNN?N  a'Classification of instrumental analyses((GB t s *ff޽h ? 33  ___PPT10g .0+]D ' ~= @B D ' = @BA?%,( < +O%,( < +D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*)t%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<**t%(D4' =%(D' =%(D' =4@BBBB%(D' =1:Bvisible*o3>+B#style.visibility<*+t%(DA' =%(D' =%(D' =A@BBBB0B%(D' =1:Bvisible*o3>+B#style.visibility<*&t%(+8+0+&t0 +_  0 v n   (    Hh?"0@NNN?N%  HDevelopment Tendency&  H ?"0@NNN?NbP- `%Higher accuracy, sensitivity, selectivity, faster and simpler (fQnx0fupOe0NN0_0{O)nWG=GGGG"D  H ?"0@NNN?NJb ~ ^(%Live organism assay   H?"0@NNN?NbU   p,%Non-destructive assay(  Hh?"0@NNN?N{ b  ^%Application of computer and stoichiometry, intelligentization of data analysis(Oo`ǑƖ pencYtvzfS 8cT > <  H$?"0@NNN?N b*  H%Multi-apparatus coupling techniques(%$  H0'?"0@NNN?Na b f"%On-line analysis(  H/̙?"6@ `NNN?N6M >PP   H2?"0@NNN?N  TChapter 2 Gas ChromatographyEH  0޽h ? 33___PPT10i.3pk+D=' ~= @B +9x] tU_y $tq!A $AġiDgQ@vw#89#"N\auA\< q*,㬏񬎬{o; ܯ߷no:|??P %˴OARE$ L(]RHW k: a+,p܃qW!יy79&AѧB-;%ӌDPsy:.yP>Xepw$LKc LjeqDvH|ߣ 7qCDr㐼@4[H?Bt$)@ `*R4k#@X)pl9HHse#U -@FgQU"njKŝ/?@ƿHgr_F}Є=o؁bP jlۉ5GR8 D镆N4 p9cNiBgbʟh?בd1Rʿ$_w 8Ƹ(`pvB>MR'Ag뿻ћ埏?@q5?Iw&wBHw_iQ;X6|55- B}ͧ3  K#]4i(4 i8lːF"]4FD79.?joZE1Z>Cja g6v`cI:b3t8牓 yqÛm >J2礟ep9R52ۘϬ(]}&o7v_vϜiGo|5QG Ut+\3!-a395 F` ={83ˍZ\4uU,&oK2<A vs{kɽ$=0fwѸt~Bv`50 v<.<f?ZٌTN̮yllٔEj_fq=q]NKĽIcKNcT4YKHHHHHHHHHHHHHZw|cnnu3/*ovLt]G{>v[`3vޯ+:X]c E\f®SyC6ɺ_WUDW1>VjUOrOQys}dc[ȇ'𰕇y5((J/~v'\=tl岕Guxm!qdBq~ߝBv0ÔC!?;$+#%ەNv`;Se_/:vr yvEgb+⇜쩍}6b#o/gWV qe #D{vb=ٖQ u'Dܞ`YbW@E(#RQE^f>SAOHH ]ohp㖯AV Z2.Po6Ш7`&X v}u 5zņ]jlLy;8W55-{Amc/"}vЋ\))6{!pQp"% %# Fґ!]4*)HHf#CT&EH7#݂i ]HCچ$/>x_v=O7"ZZbВgV珐U? 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