Attribution Non-Commercial (BY-NC)

15 views

Attribution Non-Commercial (BY-NC)

- Formula Sheet Midterm ECON 221
- Stat 201 Practice
- Independent Quality Assurance Declaration for ASEA
- Data Analysis and Fitting
- Send to Ty
- STA6166_HW2_Ramin_Shamshiri_Solution
- 6 sebaran penarikan contoh
- 新增文字文件
- tmpC387
- Session - 6 Statistics and Data Analysis
- EP101 Sen Lnt 009 Analytical Tools May11
- Accuracy
- R-manual
- HP5 GC Columns
- Asymmetric Losses
- Statistics
- 2007 exam.pdf
- 2007-01
- NDT methods on steel buildings
- 3.Questionnnaire

You are on page 1of 32

Dept. of Chemical Engineering

Hanyang Univ.

Seoul 133-791, Korea

Tel. +82-2-2220-0527

hp: http://hnp.hanyang.ac.kr

E-mail: sangman@hanyang.ac.kr

Instrumental Analysis

• Contents

1. Basics

2. Spectroscopy

3. Instrumentation

1. Basics on Chemical Analysis

Chemical Analysis

• Chemical Analysis

separation, identification, and the determination of the relative

amount of the components in a sample (analyte) of matter

1) qualitative analysis : identification of analyte

2) quantitative analysis : relative amount of analyte

1) classical analysis : the measurement of the weight or

volume of sample to be analyzed

2) instrumental analysis : the measurement of some quantity

that is proportional to the amount of analyte in that sample

Quantitative Chemical Analysis

1) weight or volume (g, ml)

2) number (moles)

3) concentration: M(molar), N(normal), F(formal), ppm, %

1) no. of moles = wt/fw

2) no. of moles = C x V

- stoichiometric relationship

aA + bB cC + dD

Classical vs. Instrumental Methods

• Classical

– Qualitative : identification by color, indicators,

boiling points, odors

– Quantitative : mass or volume

e.g. gravimetric, volumetric

• Instrumental

– Qualitative : identification by measuring physical property

e.g. spectroscopy, electrode potential,

chromatography, electrophoresis

– Quantitative : measuring property and determining

relationship to concentration

e.g. spectrophotometry, mass spectrometry

– Often, same instrumental method used for qualitative and

quantitative analysis

Types of Instrumental Methods

1) Emission

–Emission spectroscopy : fluorescence, phosphorescence,

luminescence

2) Absorption

–Absorption spectroscopy : spectrophotometry, photometry,

nuclear magnetic resonance, electron spin resonance

3) Scattering

–Turbidity, Raman

4) Refraction

– Refractometry, interferometry

Types of Instrumental Methods

6) Radiation rotation

– Polarimetry, circular dichroism

7) Electrical potential

– Potentiometry

8) Electrical charge

– Coulometry

9) Electrical current

– Voltammetry - amperometry, polarography

– Conductometry

Types of Instrumental Methods

11) Mass

– Gravimetry

– Mass spectrometry

– Stopped flow, flow injection analysis

14) Thermal

– Thermal gravimetry, calorimetry

15) Radioactivity

– Activation, isotope dilution

– (Often combined with chromatographic or electrophoretic

methods)

Steps in a Chemical Analysis

• Steps in a chemical analysis

2) sampling : representative of the bulk

3) preparing laboratory sample: small, homogeneous

4) defining replicate samples: improve the quality of results

and liability

- replicate samples: portions of a material of approximately

the same size that are carried through an analytical

procedure at the same time and in the same way

5) preparing solutions of sample

6) eliminating interferences (species other than the analyte that

affect the final measurement)

7) calibration and measurement: C(A) = kX

8) calculating results

9) evaluating results and estimating their reliability

Selecting a Method

– Precision/Accuracy

– Amount of sample

– Range of analyte concentration

– Interferences

– Physical and chemical properties of sample matrices

– Number of sample

– Time required for analysis

– Professionalism

– Availability of instrument

– Cost

Characteristics of Instrument

• Precision/Bias

• Sensitivity

• Detection limit

• Concentration range

• Selectivity

Precision and Bias

• Precision : Deviation

– Measure of random, or indeterminate error

– Reproducibility

– Standard deviation, Coefficient of Variation

– Figure of merit

• Bias : Error

– Measure of systematic or determinate error

– Bias = (population mean) – (true value)

Sensitivity

• Sensitivity

differences in analyte concentration

– Tow factors

• Slope of calibration curve - steeper slope

• Precision – better precision

Data Domains

• Data Domains

electrical signals : 정보를 코드화하는 방법들을 영역(도메인)이라고

한다

domain to another.

environment

electrical data

data

Time Domains

of a signal, but the function of signal fluctuation with time

- Time

– vary with time

– frequency, phase, pulse width

- Analog

– continuously variable magnitude

– current, voltage, charge

- Digital

– discrete values

– count, serial, parallel, number

Sensitivity

• Sensitivity

– Calibration sensitivity: S

– larger slope of calibration curve means

more sensitive measurement

• Analytical Sensitivity

– Mandel and Stiehler

– AS = slope of calibration curve/std.

deviation

– AS is unchanged with the increase in the

signal amplification of instrument, because

std. deviation also increases with the

increase in the slope of calibration curve

Detection Limit

• Minimum signal :

– Signal (min) = Average Signal of blank + ks (blank)

– From statistics k=3 or more

• (at 95% confidence level)

• Suggested by Long and Winefordner

Dynamic Range

but cannot perform reliable quantitation

– the lowest conc. limit for the measurement

– when signal is no longer proportional to concentration

Selectivity

concomitants. Best method is more sensitive to analyte than

interfering species (interferent).

– Signal = m(A)c(A) +m(B)c(B) + Signal blank

• Selectivity coefficient

– kB,A = m(B)/m(A)

selective)

Errors and Standard Deviations

• Definition

xm = Σ xi/N

the set and the smallest

measurements that have been made in exactly the same way

accepted value

Errors and Standard Deviations

• Precision

s = [ Σ (xi-xm)2/(N-1)]2

- Variance: s2

Standard Deviations

• Standard Deviation

sy = (sa2 + sb2 + sc2)1/2

sy/y = {(sa/a)2 + (sb/b)2 + (sc/c)2}11/2

cf. y = a(±sa) x a(±sa) x a(±sa),

sy/y = {(sa/a)2 + (sa/a)2 + (sa/a)2}11/2

y = log a(±sa), sy = 0.434 x (sa/a)

Significant Figures

• Significant Figures: all of the certain digits + the 1st uncertain digit

1) disregard all initial zeros

2) disregard all final zeros unless they follow a decimal point

3) all remaining digits including zeros between non-zero digits

are significant

in the original number

(mantissa; right digits of the decimal pomit,

characteristic; left digits of decimal point)

- rounding data

1) choose even or odd number

2) do not round until calculations are complete (guard digit)

Errors and Standard Deviations

• Accuracy

E = x(i) – x(t), x(t); true or accepted value

percent relative error (Er) = [x(i) – x(t)]/x(t) x 100 (%)

• Types of Errors

affect only a single result

Determinate Errors

• Sources of Determinate Errors

(non ideal physical or chemical behavior)

sample

Determinate Errors

- periodic calibration, care, and self-discipline

1) analysis of standard samples

standard reference materials (SRM)

2) independent analysis

3) blank determinations (for detecting constant errors)

4) variation in sample size

- eliminate through self-discipline

Statistical Treatments for Indeterminate Errors

• Statistical treatment of indeterminate errors

- population (universe): data exist in principle (N -> infinity )

- sample: a small set of data which represent a population

• Gaussian Distribution:

- Gaussian Curve: frequency vs. deviation from mean

Normal Error Curve: frequency vs. z {= (x- μ)/σ}

1) the mean occurs at the central point of maximum frequency

2) the symmetric distribution

3) an exponential decrease {= exp(-2z2)/(2π)1/2σ}

±1σ ; 68.3%, ±2σ; 95.5%, ±3σ; 99.7%

- standard deviation; sm = s/N1/2, σm = σ/N1/2 (for N>20, s ~ σ)

pooled standard deviation;

spooled = [(s12 + s22 + s32….)/(N1 +N2 + N3 + …. - Ns)]1/2

Statistical Treatments for Indeterminate Errors

• Gaussian Curve vs. Normal Error Curve (NEC)

0.4

Relative Frequency

0.3

0.2

0.1

0.0

-3 -2 -1 0 1 2 3

Statistical Treatments for Indeterminate Errors

around xm that probably contains μ

- standard deviation ~ σ

CL for μ = x ± z σ

for N replicate measurement, CL for μ = xm ± z σ/N1/2

- Standard deviation ~ s

CL for μ = x ± ts,

for N replicate measurement, CL for μ = xm ± ts/N1/2

Statistical Treatments for Indeterminate Errors

• Rejection of Outlyers

- T-test:

Tn = |xq – xm|/s,

for entire set including the questionable result

- Q-test:

Qexp = |xq – xn|/w, xn; the nearest neighbor of xq

Statistical Treatments for Indeterminate Errors

xm – μ = ± ts/N1/2

xm1 – xm2 = ± tspooled x [(N1 + N2)/(N1xN2)]1/2

Δxm = xm1 – xmb > tsb [(N1 + N2)/(N1xN2)]1/2

F = sA2/sB2 > 1

- Formula Sheet Midterm ECON 221Uploaded byJasonJin93
- Stat 201 PracticeUploaded byTina Flux
- Independent Quality Assurance Declaration for ASEAUploaded byJeff Moe
- Data Analysis and FittingUploaded byChu Pau Loong
- Send to TyUploaded byvee979
- STA6166_HW2_Ramin_Shamshiri_SolutionUploaded byRaminShamshiri
- 6 sebaran penarikan contohUploaded bysudahkuliah
- 新增文字文件Uploaded byapi-3811559
- tmpC387Uploaded byFrontiers
- Session - 6 Statistics and Data AnalysisUploaded byKarthik Abhi
- EP101 Sen Lnt 009 Analytical Tools May11Uploaded bySàtz ÑÖÑït
- AccuracyUploaded byPrisma Trida
- R-manualUploaded byKevin Madge
- HP5 GC ColumnsUploaded bycrackerdar
- Asymmetric LossesUploaded byRahul Sharma
- StatisticsUploaded byfayumot
- 2007 exam.pdfUploaded byElle Smart
- 2007-01Uploaded byLuminita Duta
- NDT methods on steel buildingsUploaded byUppala Krishna Chaitanya
- 3.QuestionnnaireUploaded byulab07
- Ch2 Introduce to Firing TheoryUploaded byfatihy73
- Normal Distribution Problems With SolutionsUploaded byMadhavaKrishna
- Large Sample, Central Limit, Normal Distribution.pdfUploaded byPedro Henrique Rosa
- 01408184Uploaded bysophiaaa
- andreas,1998Uploaded byAnis Ibrahim
- 3Normal Dist ProblemspdfUploaded byAjitesh Kumar
- 05165387Uploaded byMayank Gupta
- Juliana Kristanti 3203015237 a CSUploaded byVia Zsandei
- Triggs-va99Uploaded byMrinalPaul
- Espana Romero2010Uploaded byFisiocoimbra Ld

- Evidencia 2 Workshop Products and ServicesUploaded byDaniel Andres Correal
- Gas Turbines Modeling Simulation and Control Using Artificial Neural NetworksUploaded byKamil
- Purchasing/Production Planner-ManufacturingUploaded byapi-121651393
- Registration FAQUploaded byPatahul Ariffin Abas
- MSP430F543X Data SheetUploaded byStand Watie
- tmp5E42Uploaded byFrontiers
- Data Migration Good DocumentUploaded bysambit76
- Cigré 640 - A Guide for Rating Calculations of Insulated Cables.pdfUploaded byCristian Martinez
- Lotus_Notes__Configuration_Guide.pdfUploaded byArun Verma
- ChemistryUploaded bySumit Irpachi
- AiUploaded bysaisampath katru
- Geographical Studies Professor Carl Ritter of Berlin 1000000232Uploaded byGaby
- math - plickersUploaded byapi-247046378
- 6288_chap1Uploaded byaparajitbanik
- reflection chapter 4Uploaded byapi-316759148
- Field Trip Report on the Study of the Palisadoes Port Royal and the Black River WetlandsUploaded byEverton J. O. Smith
- NENA Interim VoIP Architecture for E-911 i2Uploaded byNousTekne
- Validation VMP Validation Master PlanUploaded byk.p.
- Jadual Waktu Jke Jan2011Uploaded byBudaq Ronggeng
- nlc knowdell career values chartUploaded byapi-307661965
- SAP BW - Generic Datasource Function Module (Multiple Delta Fields)Uploaded bySaikiran Raghu
- Evaluate the Relevance of Bell Hooks Gender Theory of Representation to Long Form Television DramasUploaded byCandidateNumber2093
- On Cyclic Edge-connectivity of FullerenesUploaded byKahar Wisanto
- Mouth-licking by Dogs as a Response to Emotional StimuliUploaded byLuis Antonio Buitron Ramirez
- StellaUploaded bykingmaster 89
- Maart 2012_1_Uploaded byAlexandru Paul Calugar
- Evento ReisUploaded byFabricioFa68
- A Practical Guide to Geostatistical - HenglUploaded byJorge D. Marques
- 3 Scheduling and DatesUploaded byDharma Raju
- NoteUploaded bySHINUMM