CHEM 2310

CHMS 5010
Chemical data Analysis
T1: Measurement Fundamentals
Reading:
(1) textbook (M&M, Ch1)
(2) Reference book (Ch2. Basic Tools of Analytical Chemistry)

Prof. Jianzhen YU
Chemistry Dept. HKUST
chjianyu@ust.hk
Fall 2016

Outline
Analytical problems
Errors in quantitative analysis

Types of errors
Handling systematic errors
Accuracy and precision
Absolute and relative uncertainty
Repeatability and reproducibility

Basic equipment for analytical measurements

Equipment for measuring mass
Equipment for measuring volume
Equipment for Drying samples

Significant figures
Manipulation of significant figures
Addition and subtraction
Multiplication and division
Measurements given as logarithms
2

Analytical problems
Example:Pb indrinkingwaterisharmful,especially
tochildren
Doesthistapwatersamplecontainanylead?
Whatisthelevelofleadinthissample?

Moreexamples

Lead
Antagonistic (mutually
resistant) to the
essential elements Ca,
Fe, I, and possibly Cu.

Effect of prenatal exposure

to lead on the mental
development of infants

Interfere with the

incorporation of Fe into
porphyrin precursors of
haem, producing
anaemia.
The metabolism of Pb
closely resembles that
of Ca in many aspects.
Impair uptake of I by
thyroid.

Chemical Measurement
Measurementisasetofoperationshavingthe
objectofdeterminingthevalueofaquantity.
Thesequenceofeventsthatinvolveachemical
measurementare:
1) Statetherealworldproblem;
2) Decidewhatchemicalmeasurementcanhelpanswerthat
problem;
3) Findamethodthatwilldelivertheappropriate
measurement;
4) Dothemeasurementandobtainaresult(valueand
uncertainty,includingappropriateunits);
5) Giveasolutiontotheproblembasedonthemeasurement
result.
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Why do we need to do data

analysis?
Unlessyouarejustgoingtotabulatealltheresultsyouhave
andnotmakeanyconclusions,thenyouneedsomewayto
treatyourresultstodeliverinformationtowhoeveris
interestedinyourdoingtheexperimentinthefirstplace.

Measurementuncertaintyisthecoreof
dataanalysis.

Errors in quantitative analysis -1

Isanewcompounddiscovered?
Supposewesynthesizeananalyticalreagentwhichwebelievetobeentirelynew.
Westudyitusingaspectrometricmethodanditgivesavalueof104 (onan
arbitraryunit).Oncheckingthereferencebooks,wefindthatnocompound
previouslydiscoveredhasgivenavalueabove100whenstudiedbythesame
methodinthesameexperimentalconditions.Sohavewereallydiscoveredanew
compound?

104 2
104 10
Noquantitativeresultsareofanyvalueunlesstheyare
accompaniedbysomeestimateoftheerrorsinherentinthem.
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Errors in quantitative analysis -2

Canwerejectameasurementthatlooksdifferent
fromtheotherrepeatmeasurements?
Supposeweperformatitrationfourtimesandobtainvaluesof

24.69mL,
24.73mL,
24.77mL
25.39mL.
Thefourthvalue(25.39ml)appearsmoredifferentthentheotherthree.Socan
thisfourthvaluebesafelyrejected,sothat(forexample)themeanresultis
reportedas24.73ml,theaverageoftheotherthreereadings?Instatisticalterms,
isthevalue25.39mlanoutlier?

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Errors in quantitative analysis -3

Arethetwosetsofmeasurementscomparable?
Supposewemeasurethevanadiumcontentofasteelsamplebytwoseparate
methods.

Method1:1.04% 0.07%
Method2:0.95% 0.04%
1. Arethetwoaveragevaluessignificantlydifferent,orarethey
indistinguishablewithinthelimitsoftheexperimentalerrors?
2. Isonemethodsignificantlylesserrorpronethantheother?
3. Whichofthemeanvaluesisactuallyclosertothetruth?

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Three types of errors

Grosserror
Systematicerror
Determinateerror
Alwaysthesamesign

Randomerror
Indeterminateerror
Normallydistributedwithmeanofzero
Everymeasurementhassomeuncertainty.Conclusionscanbe
expressedwithahighoralowdegreeofconfidence,butnever
withcompletecertainty.
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Gross errors
Grosserrorexamples

Completeinstrumentbreakdown
Accidentallyspillingsolution
Reagentcontamination
Miscalculations,incorrectuseofunits,conversionfactors,
orderofmagnitude(decimalplaceerrors)
Mislabellingorcrosslabellingofsamples

Grosserrorsareavoidablethroughbetterprocedures.
Scientificfraudalsoatypeofgrosserror canbedetected
sinceresultsarenotreproduciblebyothers
Theyoftenresultinoutliersinthedatawhichcanbe
identifiedandremovedbeforestatisticalanalysis.
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Monitoring ozone over the Antarctic:

Is ozone column lower than 190 DU possible or
instrument error?
The typical ozone column abundance is 290 to 310
DU over the globe.
The British Antarctic Survey has been monitoring,
for many years, the total column ozone levels at
its base at Halley Bay in the Antarctica.
Monitoring data indicate that column ozone levels
have been decreasing since 1977.
NASAs satellite (TOMS-Total Ozone Mapping
Spectrometer) records ozone column lower than
190 DU
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ftp://toms.gsfc.nasa.gov/pub/nimbus7/images/spole/Y1983/IM_ozspl_n7t_19831102.png
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Random vs. systematic errors-1

Four students (AD) each perform an analysis in which exactly 10.00 ml of
exactly 0.1 M NaOH is titrated with exactly 0.1 M HCl. Each student performs five
replicate titrations, with the results shown in the table below.

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Random vs. systematic errors-2

All too high, small spread

Avg: 10.01, large spread

Avg: 9.90, large spread

Avg: 10.01, small spread

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Causes for systematic error

Systematicerror
Acolorblindpersonmightpersistentlyoverestimatetheendpointina
titration,
Theextractionofananalyte fromasamplemayonlybe90%efficient,
Thederivatization stepbeforeanalysisbyGCmaynotbecomplete.
.
Ineachofthesecases,iftheresultswerenotcorrectedfortheproblems,
theywouldalwaysbewrong,andalwayswrongbythesameamountfora
particularexperiment.
Systematicerrorcanbeestimatedbymeasuringareferencemateriala
largenumberoftimes.Thedifferencebetweentheaverageofthe
measurementsandthevalueofthereferencematerialisthesystematic
error.
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Causes for random error

Randomerrorarisesfromtheeffectsofuncontrolled (and
maybeuncontrollable)variablesinthemeasurement.

theinabilityoftheanalysttoexactlyreproduceconditions,
fluctuationsintheenvironment(temperature,pressure),
roundingofarithmeticcalculations,
briefgustsofwind,
ashakeoftheanalystshand.
randomelectricalnoiseinaninstrument.
.

Randomerrorhasanequalchanceofbeingpositiveornegative.
Itisalwayspresentandcannotbecorrected(thoughmaybe
reduced)
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Example: Causes for systematic

and random errors
Pleaseidentifythreecontributingfactorsto
themeasurementerrorandcharacterize
theirnature(systematicvs.random)

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Difference between the three

types of errors

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Summary:SystematicandRandomerrors

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Accuracy and Precision

Accuracyishowcloselythe
resultofanexperiment
agreeswiththetrueor
expectedresult.
Precisionisameasureof
variabilityofrepeat
measurements

Precision describes random error, bias describes systematic error and the
accuracy, i.e. closeness to the true value of a single measurement or a
mean value, incorporates both types of error.
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Accuracy: Absolute and percent

relative error
Absoluteerror

Percentagerelativeerror

24

Precision: Absolute and Relative Uncertainty

Absolute uncertainty
expresses the margin of uncertainty in a measurement
e.g. 0.02 mL for a calibrated buret
Relative uncertainty
compares the absolute uncertainty with quantity being measured
e.g for buret reading 12.35 0.02 mL
Percent relative uncertainty (0.02 mL /12.35 mL)x100% = 0.2%
(note only 1 sig fig)

If absolute uncertainty in a buret reading is 0.02 mL

then the % relative uncertainty is
2% for a 1 mL reading
0.2% for a 10mL reading
0.1% for a 20mL reading

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Repeatability and reproducibility

Repeatabilitydescribestheprecisionofwithinrun
replicates.
Reproducibilitydescribestheprecisionofbetween
run replicates.
Thereproducibilityofamethodisnormallyexpected
tobepoorer(i.e.withlargerrandomerrors)thanits
repeatability.

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Repeatability and reproducibility

measurements -1
Whentheanalyticalmethodwasfirstestablished,methodvalidationwillhave
determinedrepeatabilityandreproducibilitystandarddeviations.

Therepeatabilitystandarddeviationisdefinedas:
Theprecisionofamethodexpressedasthestandarddeviationof
independentdeterminationsperformedbyasingleanalystusing
thesameapparatusandtechniques.
independentmeasurementsmeansthatanumberofseparatetest
portionsshouldbeweighed,dissolved,andmeasured,notthatthesame
solutionshouldbepresentedtotheanalyticalinstrumentanumberof
times.
Ifthisweretobedonethestandarddeviationofthesemeasurement
resultswouldbetherepeatabilityoftheinstrumentmeasurement,not
therepeatabilityoftheanalysis.

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Repeatability and reproducibility

measurements -2
Thereproducibilitystandarddeviationisdefinedas:
Theprecisionofamethodexpressedasthestandarddeviationof
determinationsperformedindifferentlaboratories.
Experiencehasshownthattheinterlaboratory reproducibilityisabout
twotothreetimestherepeatability
reproducibilityissometimesusedtorefertothestandarddeviationof
measurementresultsobtainedwithinthesamelaboratory,butperhaps
bydifferentanalystsand/ordifferentequipmentand/ordifferentdays.

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Basic Equipment for Analytical

Measurements

29

Equipment for measuring mass

Left photo: A typical digital electronic
balance capable of determining mass to
the nearest 0.1 mg. The sticker inside
the balances wind shield is its annual
calibration certification.

30

Measurement errors: mass

Whats the mass of a fingerprint?

Materials being weighed should normally be

handled using tongs or laboratory tissues.

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Systematic errors in mass

measurements -1
Possiblecauses
Aweightiswithinthetolerancelimits,butnotofexactlythecorrect
weight.
Adsorptionofmoistureonthesurfaceoftheweighingvessel
Corrodedordustcontaminatedweights
Thebuoyancyeffectoftheatmosphere,actingtodifferentextentson
objectsofdifferentdensity.

Minimizingsystematicerrors
Calibrateweightsagainststandardsprovidedbystatutorybodiesand
authorities(seeabove).Thiscalibrationcanbeveryaccurateindeed,
e.g.to0.01mgforweightsintherange110g.
Takesomesimpleexperimentalprecautions,e.g.,weighingby
differencecancelssystematicerrorsarisingfromthemoistureand
othercontaminantsonthesurfaceofthebottle.
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Systematic errors in mass

measurements -2
Inmostvolumetricexperimentsweighingerrorswillprobably
benegligible comparedwiththevolumetricones.
Gravimetricmethodsareusuallyusedforthecalibrationof
itemsofvolumetricglassware,byweighing(instandard
conditions)thewaterthattheycontainordeliver,
standardsfortopqualitycalibrationexperimentsaremadeup
byweighingratherthanvolumemeasurements.

33

Equipment for measuring volume:

Burets, pipets & Volumetric Flasks

Volumetric glassware is usually calibrated to contain (TC) or to deliver (TD)

particular volume at 20oC

Whats the volume of a drop?

34

Calibrated to deliver (T.D.) or to contain (T.C.)

Close-up of the 10-mL transfer pipet

This label indicates that the

pipet is calibrated to deliver
(T. D.) 10 mL of solution with an
uncertainty of 0.02 mL at a
temperature of 20oC.
to deliver: Do not blow out the last drop.
Glass expands and contracts with changes
in temperatures. At higher or lower
temperatures, the pipets accuracy is less
than 0.02 mL.

A volumetric flask has

similar markings, but uses
the abbreviation T. C. for to
contain in place of T. D.
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Tolerances of Volumetric Flasks

Obviously there is an inherent error - flasks cannot have perfect volume

The guaranteed variability of range (or tolerance) is shown; this is not a standard deviation
Note that % errors tend to be larger for smaller volumes
If a 10-mL volumetric pipet has a tolerance of 0.02 mL, this means that the pipet
delivers an actual volume within the range 9.9810.02 mL at a temperature of 20oC.
Also, you should record 4 significant figures in your notebook (i.e., 10.00 mL).
36

Tolerances of Pipets

Calibration
mark

Transfer
pipet

Mohr
measuring
pipet
37

Measurement Errors: Volume -1

Infillinga250mlstandardflasktothemark,the
error(i.e.thedistancebetweenthemeniscusand
themark)mightbeabout0.03 cminaflaskneckof
diameterca.1.5 cm.
Thiscorrespondstoavolumeerrorofabout0.05ml
(0.7520.030.05mL)
only0.02%ofthetotalvolumeoftheflask.
Inreadingaburette(theconventionaltypegraduated
in0.1mldivisions),theerroris~0.010.02ml.
(0.520.030.02mL)
Eachtitrationinvolvestwosuchreadings(theerrorsof
whicharenotsimplyadditive seeerrorpropagation);
Ifthetitrationvolumeisca.25ml,thepercentage
errorisagainverysmall.
Theexperimentshouldbearrangedsothatthe
volumeoftitrantisnottoosmall(not<10ml),
otherwisesucherrorsmaybecomeappreciable.
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Measurement Errors: Volume -2

Sourceofsystematicerrors

Thedrainageerrorsintheuseofvolumetricglassware,
calibrationerrorsintheglassware
indicatorerrors.
Temperatureeffects.
V.equipmentisconventionallycalibratedat20C,butthelab
temperaturemayeasilybeseveraldegreesdifferentfrom
this.Manybiochemicalanalysisarecarriedoutincoldrooms
atca.4C.
Thetemperatureaffectsboththevolumeoftheglassware
andthedensityofliquids.

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Example: Calibrate a Buret

50 mL buret

tolerance 0.05 mL (manufacturer)

measured: 29.43 mL is this accurate ?

Construct a calibration curve!

correction factor is -0.03 mL: the measured 29.43 mL should be corrected to 29.40 mL
40

Digital Micropipettors: for dispensing < 1mL liquid

Micropipets are designed to deliver volumes of 1 to 1000 L (i.e less than 1

mL) and useful in many biochemical experiments. Plastic tips are
disposable. In adjustable cases, volume is set by a dial.

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Glass microsyringes

Source:
http://www.hamiltoncompany.com
/products/syringes/c/148/

42

Equipment for drying samples

Manymaterialsneedtobedriedpriortoanalysistoremoveresidualmoisture.

Example of a muffle
furnace.

Example of a desiccator.
The solid in the bottom of the
desiccator is the desiccant,
which in this case is silica gel.

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Significant Figures
Significantfigures:theminimumnumberofdigitsrequiredto
expressavalueinscientificnotationwithoutlossofprecision.
Thenumberofsignificantfiguresinameasurementisthenumberofdigitsknown
exactlyplusonedigitwhosevalueisuncertain.

Second scenario:
Suppose we weigh a second
cylinder, using the same balance,
obtaining a mass of 0.0990 g.
Does this measurement have 3, 4,
or 5 significant figures?
When weighing an object on a balance, the
measurement fluctuates in the final
decimal place. We record this cylinders
mass as 1.2637 g 0.0001 g.

44

Significant Figures and Zeroes

One difficulty is with zeros to decide whether they are significant or not.
They are significant if
a) They are in between other digits or
b) They lie at the end on right hand side of a decimal point

Examples of significant zeroes in bold sig figs in green

106

0.0106

0.106

0.1060

How many sig figs in numbers below ?

a) 1.0903

b) 0.039 10 c) 1.40 x 104

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Counting significant figures

Example:Statehowmanysignificantfiguresthereareinthefollowing
measuredamounts.
1.Theconcentrationofcopperintapwaterwas0.00000572M
2.Theconcentrationofglucoseinbloodwas5.0mM
3.Themassofammoniumnitratewas5.20tonnes

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Significant Figures: more examples

6.302 x 10-6 = 0.000 006 302 which has 4 sig. Figs.

92 500 is ambiguous could be:
9.25 x 104

3 sig figs

9.250 x 104

4 sig figs

9.2500 x 104 5 sig figs

You should write one of these three numbers, instead of
92 500, to indicate how many figures are actually known.

The last significant figure in a measured quantity always has associated

uncertainty. The minimum uncertainty is 1 in the last digit.
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Are the numbers

real?

48

Interpolation and Significant Figures

from a Measurement

Scale from a spectrometer is shown the absorbance appears to be 0.234

This is 3 sig figs. The 2 and 3 are certain but the 4 is estimated as 1
The % transmittance is around 58.3, also 3 sig figs, but uncertainty ca. 0.2.
49

A split second: Are we

splitting hairs?
Euro Men's 100m final 2010
1. Christophe Lemaitre (Fra) 10.11secs
2. Mark Lewis-Francis (GB) 10.18
3. Martial Mbandjock (Fra) 10.18
4. Francis Obikwelu (Por) 10.18
5. Dwain Chambers (Gbr) 10.18
6. Jaysuma Saidy Ndure (Nor) 10.31
7. Emanuele Di Gregorio (Ita) 10.34
coolfwdclip.blogspot.com

In an European athletics final of 100m the winner was clear, but 2nd to 5th were
all the same time to 100th second ! As scientist seems clear they all did the same
since differences in lane, start etc lead to random error on this order of magnitude
Q: At their speed what is the distance represented by 1/1000th second ?
Speed = 100m/10.2 s= 10m/s, 10m/s x 0.001 = 0.01 m =1 cm

50

Manipulation of Significant Figures

Rounding should be done only on final answer (not intermediate
results) to avoid accumulating round off errors.
How many digits should be retained in answer after arithmetic operations
involving sig figs ?

Addition and Subtraction

If values go to same decimal place answer also goes to same decimal place
1.362 x 104
3.111 x 104 +
_________
4.473 x 104

5.345
6.728 +
_____
12.073

7.26 x 1014
6.69 X 1014 _
________
0.57 X 1014

Note these answers have same, more or less sig. figs than original values
51

Addition and Subtraction II

If values do not have same uncertainty level in decimal place,
The answer is limited by the least certain of them
For example in calculating molecular masses, the atomic weights of
elements have different levels of precision
For perchloric acid HClO4 the precision in molecular mass limited by Chlorine
H
Cl
O

1.00794
35.453
15.999 4 (x4) +
_______
100.458 54
Note the final number should then be
rounded up to 100.459

Q: What about round off if last two digits had been 50 not 54 ?
52

Rounding off Significant Figures

53

Challenge Show that the answer has four significant figures even if all
numbers are expressed as multiples of 104 instead of 105.

Significantdigitscanbegainedorlostthrough
addition/subtractionmanipulations.
54

Loss of Sig Figs through subtraction

Example: Back titration
3.2 Silver Ion Titration (5pts)
10.00 mL of 0.500 7 M silver nitrate solution (excess) is added to 10.03 mL of a chloride
solution of approximately 0.1M. The excess silver is then back-titrated via the Volhard
method using 8.20 mL of 0.501 0 M potassium thiocyanide.
What is the concentration of the chloride in the original unknown ?
Give the appropriate number of significant figures

Initial mmol Ag+

Excess Ag+
Difference
Cl- concentration

= 10.00(4sf) x 0.5007(4sf) = 5.007 mmol (4sf)

= 8.20(3sf) x 0.5010(4sf) = 4.1082 mmol (3sf)
= 5.007(4sf) 4.1082(3sf) = 0.8988 mmol (2sf)
= 0.8988 (2sf) / 10.03 (4sf) = 0.0896 M (2sf)

Answer = 0.090 M (2sf)

Multiplication
Multiplication
Subtraction
Division

The subtraction sig fig is based on decimal place

55

Sig Figs : Multiplication and Division

Note the difference with addition /subtraction where decimal place

is the important issue
56

Molecular Mass revisited !

Implication: if mass of one H atom has uncertainty in 5th decimal place

then the uncertainty for 10 H atoms should be in 4th decimal place

57

Sig Figs: Exact numbers

Anexactnumberhasaninfinitenumberof
significantfigures.
Stoichiometriccoefficientsareoneexampleofanexact
number.
Anotherexampleofanexactnumberistherelationship
betweensomeunits.Forexample:Thereareexactly1000
mLin1L.Boththe1andthe1000haveaninfinitenumber
ofsignificantfigures.

58

Sig Figs: One Tricky Example

First a simple but deceptive one
True/ False (2pts)
If the pH of a solution is 3.72; the [H+] concentration is known to 3 sig figs
Simple response is that H conc is related to pH and the pH value given to 3 digits
so answer is true, right ?
Why ?

pH is log [H+].

Converting the pH number to a conc. is like taking an antilog and we have seen that the first
digit is just the decimal place marker

Answer from calculator is 1.905 x 10-4 but should be to 2 sig figs and so 1.9 x 10-4
Note: the 1.9 comes from the .72 and the 10-4 from the value of 3.

59

Sig Figs for measurements given as logarithms

For a measurement given as a logarithm, such as pH, the number of significant
figures is equal to the number of digits to the right of the decimal point.
Digits to the left of the decimal point are not significant figures since they only
indicate the power of 10.
A pH of 2.45, therefore, contains two significant figures.

Proper use of sig figs (bold /green) in log /anti-log conversions shown below
log 0.001 237 = -2.907 6

antilog 4.37 = 2.3 x 104

log 1 237 = 3.092 4

104.37 = 2.3 x 104

60

log 3.2 = 0.51

10-2.600 = 2.51 x 10-3

Significant figures in pH and pK values

p-function: A function of the form pX, where pX=-log(X).
When working with concentrations or other values that span many orders of
magnitude, it is often more convenient to express the concentration/value
as a p-function.

pH log[ H ]
Note a pH of 7.22 implies only two significant figures, not three.
The 7 is an order of magnitude indicator, i.e., power of 10.

pK log K

61

Sig Figs: Another Tricky Example

62

The Real Rule for Significant Figures

The first uncertain figure of the answer is the last significant figure.

If we rounded the answer to three digits, it would be 1.02(0.00), which

loses all information about the uncertainty. We need to keep enough
digits to meaningfully represent the uncertainty.
63

Homework T1
Textbook, Ch1. #1, #2, #5

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