Section 03

Data Handling and Spreadsheets in

Analytical Chemistry
 Why do we need statistics in
analytical chemistry?
• Scientists need a standard format to
communicate significance of experimental
numerical data.
• Objective mathematical data analysis
methods needed to get the most information
from finite data sets
• To provide a basis for optimal experimental
design.
 What Does Statistics Involve?
• Defining properties of probability
distributions for infinite populations
• Application of these properties to
treatment of finite (real-world) data sets
• Probabilistic approaches to:
– Reporting data
– Data treatment
– Finite sampling
– Experimental design
 Some Useful Statistics Terms
• Mean – Average of a set of values
• Median – Mid-point of a set of values.
• Population – A collection of an infinite munber of
measurements. N  infinity
• Sample – A finite set of measurements which
represent the population.
• True value (true mean)- (), mean value for the
population.
• Observed Mean –(x), mean value of the sample set
 Accuracy and Precision:
Is There a Difference?
• Accuracy: degree of agreement between
measured value and the true value.
• Absolute true value is seldom known
• Realistic Definition: degree of agreement
between measured value and accepted true
value.
 Precision
• Precision: degree of agreement between
replicate measurements of same quantity.
• Repeatability of a result
• Standard Deviation
• Coefficient of Variation
• Range of Data
• Confidence Interval about Mean Value
 You
Youcan’t
can’thave
haveaccuracy
accuracywithout
withoutgood
goodprecision.
precision.
But
Butaaprecise
precise result
resultcan
canhave
haveaadeterminate
determinateor
orsystematic
systematicerror.
error.

Fig. 3.1. Accuracy and precision.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Determinate Errors
Are They Systematic?
• Determinate Errors:
• Determinable and either avoided or
corrected.
• Constant errors
• Uncalibrated weights
• Burets- volume readings can be corrected
• Concentration variation with temperature
 Indeterminate Errors
Are They Random?
• Indeterminate Errors-
– accidental or random errors
• Represent the experimental uncertainty that
occurs in any measurement.
– Small difference on successive measurements
• Random Distribution
• Mathematical Laws of Probability
• Normal distribution or Gaussian Curve
Random
Randomerrors
errorsfollow
followaaGaussian
Gaussianorornormal
normaldistribution.
distribution.
We
Weare
are95%
95%certain
certainthat
thatthe
thetrue
truevalue
valuefalls
fallswithin
within2σ2σ(infinite
(infinitepopulation),
population), IF
IF
there is no systematic error.
there is no systematic error.

©Gary Christian,
Analytical
Chemistry,
6th Ed. (Wiley)
Fig. 3.2 Normal error curve.
 A Review of Significant Figures
How many significant figures in the following
examples?
• 0.216 90.7 800.0 0.0670 500
• ((35.63 * 0.5482 * 0.05300)/1.1689)*100%
• 88.5470578%
• 88.55%
• ((97.7/32.42)*100.0)+36.04)/687
• 0.4911
 Ways of Expressing Accuracy
• Absolute Errors: difference between true
value and measured value
• Mean Errors: difference between true
value and mean value
• Relative Error: Absolute or Mean Errors
expressed as a percentage of the true value
 -x)/Relative Error
• Relative Accuracy: measured or mean
value expressed as a percentage of true
value
((x/Relative Accuracy
 Standard Deviation
The Most Important Statistic
• Standard Deviation  of an intinite set of
experimental data is theoretically given by

 xi – 

• xi = individual measurement
 mean of infinite number of
measurements (true value)
• N = number of measurements
Standard Deviation of a Finite Set
of Experimental Data
• Estimated Standard Deviation, s (N < 30)
• sxi – x
• For finite sets the precision is represented
by s.
• Standard deviation of the mean smean
• Smean = s/N
• Relative standard deviation rsd: or
coefficient of variation
• (s/mean)*100 = % rsd
 Enter
Entertext,
text,numbers,
numbers,or
orformulas
formulasin
inspecific
specificcells.
cells.

Fig. 3.3. Spreadsheet cells.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

The
Theformula
formulainincell
cellB6B6subtracts
subtractsthe
theweight
weightofofthe
theflask
flaskfrom
fromthe
theweight
weightwith
withwater.
water.
You
Youcan
cancopy
copythe
theformula
formulato tothe
theright
rightby
byhighlighting
highlightingthe
thecell
celland
anddragging
draggingititfrom
fromthe
the
lower
lowerright
rightcorner
cornerto tothe
theright.
right.

Fig. 3.4. Filling cell contents.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
WeWeoften
oftenuse
userelative
relativecell
cellreferences
referencesin informulas.
formulas.
IfIfaanumber
numberfrom
fromaagiven
givencell
cellisisto
tobe
beaaconstant
constantininthe
theformula,
formula,place
place$$in
infront
frontof
ofthat
that
cell’s
cell’sdescriptors.
descriptors.

©Gary Christian,
Fig. 3.5. Relative and absolute cell references. Analytical Chemistry,
6th Ed. (Wiley)
Excel
Excelhas
hasaanumber
numberof ofmathematical
mathematicaland
andstatistical
statisticalfunctions.
functions.
Click
Clickon
onfxf on
onthe
thetool
toolbar
barto
toopen
openthe
thePaste
PasteFunction.
Function.
x

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 The
Thecell
cellB4
B4formula
formulacalculates
calculatesthe
thestandard
standarddeviation
deviationof
ofcells
cellsB1
B1to
toB3.
B3.

Standard deviation calculation.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
 Propagation of Errors
Not Just Additive
Computation Determinate Indeterminate
(Random)
Add/Subtract ER = EA+ EB-EC sR2 = sA2+ sB2+sC2
R = A+B-C sR =sA2+ sB2+sC2
Multiply/Divide ER= EA+ EB- EC (sR/R)2 =(sA/A)2+
R = AB/C R A B C (sB/B)2+(sc/C)2
General
R = f(A,B,C,…)
 Control Charts
• Quality control chart: time plot of a
measured quantity assumed to be constant.
• Inner and Outer control limits
• Inner control limit: 2
• Outer control limit: 2.5 or
3
This
Thisisisaatime
timeplot
plotfor
foranalysis
analysisof
of the
thesame
samesample,
sample,assumed
assumedto
tohave
haveonly
only
random
randomdistribution,
distribution,to
tocheck
checkfor
forerrors
errorsin
inaamethod.
method.
At
At2there
2thereisisaa11in in20
20chance
chanceaavalue
valuewill
willexceed
exceedthis
thisonly
onlyby
bychance.
chance.
At2.5,
At2.5,ititisis11in
in100.
100.

Fig. 3.6. Typical quality control chart.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Confidence Limit
How sure are you?
• Confidence Limit = x ± ts/
t statistical factor that depends on the number
of degrees of freedom
 degrees of freedom = N-1

Values of t at different confidence levels and

degrees of freedom are located in table 3.1
Select
Selectaaconfidence
confidencelevel
level(95%
(95%isisgood)
good)for
forthe
thenumber
numberof
ofsamples
samplesanalyzed
analyzed
(=
(=degrees
degreesof
offreedom
freedom+1).
+1).
Confidence
Confidencelimit
limit==xx±±ts/√N.
ts/√N.
ItItdepends
dependson
onthe
theprecision,
precision,s,s,and
andthe
theconfidence
confidencelevel
levelyou
youselect.
select.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Tests of Significance
Is there a difference?
• The F Test
• Designed to indicate whether there is a
difference between two methods.
• F = s12/s22 degrees of freedoms 1 and 

If calculated F value exceeds a tabulated F

value at a selected confidence level, then
there is a significant difference between the
variances of the two methods.
 FF==ss12/s
2 2 .2
/s
2
1 2 .

You
Youcompare
comparethethevariances
variancesof
oftwo
twodifferent
differentmethods
methodstotosee
seeififthere
thereisisaa
significant
significantdifference
differencein
inthe
themethods,
methods,atatthe
the95%
95%confidence
confidencelevel.
level.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Student T Test
Are there Differences in the Methods?
1. t Test When an Accepted Value is Known
x ± ts/
It follows
±t = (x- s
Select
Selectaaconfidence
confidencelevel
level(95%
(95%isisgood)
good)for
forthe
thenumber
numberof
ofsamples
samplesanalyzed
analyzed
(=
(=degrees
degreesof
offreedom
freedom+1).
+1).
Confidence
Confidencelimit
limit==xx±±ts/√N.
ts/√N.
ItItdepends
dependson
onthe
theprecision,
precision,s,s,and
andthe
theconfidence
confidencelevel
levelyou
youselect.
select.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Tests of Significance
Is there a difference?
• Comparison of the Means of Two Samples
• ±t = ((x1-x2)/sp) ))

• pooled standard deviation: sp

• sp = xi1-x1)2+(xi2-x2)2+…+xik-xk)2/(N-k))
 Rejection of a Result:
The Q Test
• The Q test is used to determine if an
“outlier” is due to a determinate error. If it
is not, then it falls within the expected
random error and should be retained.
• Q = a/w
• a = difference between “outlier” and nearest
sorted result
• w = range of results.
QQCalc ==outlier
outlierdifference/range.
difference/range.
Calc

IfIfQQCalc >>QQTable, ,then reject the outlier as due to a systematic error.

Calc Table then reject the outlier as due to a systematic error.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 Confidence Limits Using Range
• Confidence Limit = x ±Rtr
The
Themedian
medianmay
maybe
beaabetter
betterindicator
indicatorof
ofthe
thetrue
truevalue
valuethan
thanthe
themean
meanfor
for
small numbers of observations.
small numbers of observations.

And
Andthe
therange
rangetimes
timesaafactor
factor(K)
(K)may
maybe
beaabetter
bettermeasure
measureof
ofspread
spreadthan
thanthe
the
standard deviation (s = RK ).
standard deviation (sr = RKR ).
r R

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

AAleast-squares
least-squaresplot
plotgives
givesthe
thebest
beststraight
straightline
linethrough
throughexperimental
experimentalpoints.
points.
Exel
Exelwill
willdo
dothis
thisfor
foryou.
you.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
Fig. 3.7. Straight-line plot.
This
ThisExcel
Excelplot
plotgives
givesthe
thesame
sameresults
resultsfor
forslope
slopeand
andintercept
interceptas
ascalculated
calculatedin
inthe
theexample.
example.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Fig. 3.8. Least-squares plot of data from Example 3.21.

 Chart
ChartWizard
Wizardisison
onyour
yourtool
toolbar
bar(the
(theicon
iconwith
withvertical
verticalbars).
bars).
Select
SelectXY
XY(Scatter)
(Scatter)for
formaking
makingline
lineplots.
plots.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)
You
Youmay
mayinsert
insertthe
thegraph
graphwithin
withinthe
thedata
datasheet
sheet(Sheet
(Sheet1),
1),or
oraanew
newSheet
Sheet2.2.

Fig. 3.9. Calibration graph inserted in spreadsheet (Sheet 1).

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)
Select
SelectLINEST
LINESTfromfromthe
thestatistical
statisticalfunction
functionlist
list(in
(inthe
thePaste
PasteFunction
Functionwindow
window ––
click on f in the tool bar to open).
click on xf in the tool bar to open).
x

LINEST
LINESTcalculates
calculateskey
keystatistical
statisticalfunctions
functionsfor
foraagraph
graphor
orset
setof
ofdata.
data.

©Gary Christian,
Analytica Chemistry,
6th Ed. (Wiley)
Fig. 3.10. Using LINEST for statistics.
Calibration Data for a Chromatographic Method
for the Determination of Isooctane in a Hydrocarbon Mixture
Mole % Peak
Isooctane Area Statistics
0.352 1.09 Slope 2.09 0.26 Intercept
0.803 1.78 Std Dev 0.13 0.16 Std Dev
1.08 2.60 R2 0.99 0.14 Std Error of Estimate
1.38 3.03 F 241.15 3.00 Degree Freedom
1.75 4.01 Sum sq regression 5.02 0.06 Sum Sq Residuals
 Peak Area vs Mole % Isooctane

4.50 PA = 2.0925Mole% + 0.2567

4.00 R2 = 0.9877
3.50
Peak A rea

3.00
2.50
2.00
1.50
1.00
0.50
0.00
0 0.5 1 1.5 2
Mole % Isooctane
 Detection Limits
There Is No Such Thing as Zero
• All instrumental methods have a degree of noise
associated with the measurement that limits the
amount of analyte that can be detected.
• Detection Limit is the lowest concentration level
that can be determined to be statistically different
from an analyte blank.
• Detection Limit is the concentration that gives a
signal three times the standard deviation of the
background signal.
 AA“detectable”
“detectable”analyte
analytesignal
signalwould
wouldbebe12
12divisions
divisionsabove
aboveaaline
line
drawn through the average of the baseline fluctuations.
drawn through the average of the baseline fluctuations.

Fig. 3.11. Peak-to-peak noise level as a basis for detection limit.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)