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Dr.GangWang Dr.DavidK.

Ryan DepartmentofChemistry UniversityofMassachusettsLowell

List Price $162 UML Bookstore $231? Internet as low as $85 ? Fifth edition 1998 Sixth ed. just out 2007 Excellent reference book

Website
http://faculty.uml.edu/David_Ryan/84.314/ Syllabus=coursedescription Schedule Materials=LectureSlides, Handouts,Videosfrom lastyear

Skoog Chapter1 Introduction


BasicsofInstrumentalAnalysis
PropertiesEmployedinInstrumentalMethods NumericalCriteria FiguresofMerit

Nobel Prizes
William H. Bragg Francis W. Aston Friderik Pregl analysis of crystal structure by means of X-rays(physics) for his discovery, by means of his mass spectrograph, of isotopes (Chemistry) invention of the method of micro-analysis of organic substances (Chemistry) his research on electrophoresis and adsorption analysis, especially for his discoveries concerning the complex nature of the serum proteins (Chemistry) development of new methods for nuclear magnetic precision measurements and discoveries (Physics) Invention of partition chromatography (Chemistry) discovery and development of the polarographic methods of analysis (Chemistry) development of radioimmunoassays of peptide hormones (Physiology or Medicine) contribution to the development of high-resolution electron spectroscopy (physics) design of the scanning tunneling microscope (physics) 1915 1922 1923

Arne Tiselius Felix Bloch Edward M. Purcell Archer J P Martin Richard L M Synge Jaroslav Heyrovsky Rosalyn Yalow Kai M. Siegbahn Gerd Binnig Heinrich Rohrer

1948

1952 1952 1959 1977 1981 1986

Colors Boiling or Melting Points Precipitation Classical Extraction Distillation Solubilities Odors Optical Gravimetric Analytical Methods Volumetric Physical Properties Conductivity Instrumental Electrode Potential Light Absorption or Emission Mass-to Charge ratio Fluorescence Chromatographic Electrophoretic

Instruments for Analysis

Performance Characteristics Of Instruments

Precision
The precision ofa measurement system,also called reproducibilit y or repeatability,is thedegreetowhich repeated measurements underunchanged conditionsshowthe same results.

accuracy of a measurement system is the degree of closeness of measurements of aquantity to its actual (true) value.

Bias Biasprovidesameasureofthesystematic,ordeterminate,error ofan analyticalmethod. = Where isthepopulationmeanfortheconcentrationofananalyte isthetruevalue Sensitivity Sensitivityofamethodorinstrumentisameasureofitsabilityto discriminatebetweensmalldifferences. Twofactorslimitsensitivity
Theslopeofcalibrationcurve Reproducibilityorprecisionofthemeasuringdevice S=mc+Sbl

Detectionlimit Minimumconcentrationormassofanalytecanbedetectedata knownconfidencelevel Sm=Sbl +ksbl Usually,k=3

Dynamicrange

LOQlimitofquantitation LOLlimitoflinearity Dynamicrangeshouldbeatleastafewordersofmagnitude

Selectivity Selectivityreferstothedegreetowhichthemethodis freefrominterferencebyotherspeciesinsample

Calibration of instrumental method


Calibrationdeterminesthe relationshipbetweenanalytical responseandanalytical concentration. 1.externalstandardcalibration
Nointerferenceeffects Obtainresponsesignalasa functionofknownanalyte concentration

Calibration of instrumental method


2.Standard additional methods Addingoneormore incrementsofstandard solutiontosample aliquots Sx=K1Cx ST =K1(Cx+Cs) Cx=CsSx/(ST Sx) WhenST =0 Cx=Cs

Calibration of instrumental method


3.internalstandard method Addaconstant amountofsubstance toallsamples,blanks, andcalibration standard. Plotratioofanalyte signalandinternal standardasafunction ofanalyte concentration.
Homework: P23 1-10

Skipthefollowing chapters
Chapter2 ElectricalComponentsandCircuits Chapter3 OperationalAmplifiersinChemical Instrumentation Chapter4 DigitalElectronicsandMicrocomputers

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Skoog Chapter5 SignalsandNoise


SignaltoNoiseRatio Allinstrumentalmeasurementsinvolveasignal Unfortunatelyallsignalshavenoisepresent Sometimesthenoiseislarge Sometimesitissosmallyoucantseeit Noiseisconstantandindependent,smallsignal largenoise S/Nisveryimportant

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Currentmeasurements (a)withnoise, (b)withnoiseaveragedout

Noise is often constant and independent of signal20

SignaltoNoiseRatio(S/N)
Parameterdescribingqualityofdata Oftenreferredtoasfigureofmerit Smeanofsignalx1 = = = NstandarddeviationsRSD RSD=relativestandarddeviation ImpossibletodetectasignalwhenS/Nlessthan2or3

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NMR spectra for Progesterone A) S/N = 4.3 B) S/N = 43

Very little confidence in ability to determine peaks at lower S/N Detection Limit
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SourcesofNoise
Chemicalnoise temp,pressure,humidity,etc. fluctuations=uncontrolledvariables Instrumentalnoise noise frominstrumental components
Thermalnoise(Johnsonnoise) thermalmotionof electronsinloadresistor Voltagefluctuation vrms =4kTRff =1/3tr Narrowbandwidthtodecreasenoise,butinstrument willbeslower
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Instrumentalnoise
Thermalnoise vrms =4kTRf vrms =rootmeansquarenoisevoltage k=Boltzmannconstant1.38x1023 J/K T=temperature R=resistance f=frequencybandwidthofnoise

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Instrumentalnoise
Shotnoise movementof electronsacrossajunction irms =2ief irms =rootmeansquarecurrentfluctuation i=averagecurrent e=chargeonelectron f=frequencybandwidth

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Instrumentalnoise
Flickernoise anynoise thatisinversely proportionaltosignal 1/f Significantatlowfrequency(<100Hz) Environmentalnoise compositeof manynoisesources e.g.anyelectricaldevicegivesoff EM(electromagneticradiation) ELFradiation=healthcontroversy instrumentsmaypickupsignals

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Environmentalnoisesources (notefrequencydependence)

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ImprovingS/N
hardware&software
Hardware
Grounding&shielding Faradaycage Analogfiltering RCfiltering Modulation convertDCsignaltohighfrequencyAC thendemodulate Signalchopping rotatingwheeltodifferentiatee.g.IR sourcefromheat Lockinamplifiers

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Primitive Faraday Cage for shielding instruments from EM Radiation must be grounded
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Analog Filtering or RC Filtering


Noisy data

RC filter

R
Filtered data

C
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Modulation

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Signalchoppinginan IRspectrophotometer

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Chopperamplifier

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ImprovingS/N
hardware&software
Software
Ensembleaveraging addingspectra Boxcaraveraging Digitalfiltering movingwindow,slidingaverage Correlationmethods

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Ensemble averaging i.e.adding oraveraging signal


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Boxcaraveraging
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