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Every measurement carries some degree of uncertainty no matter how good the measurement process can be. The
uncertainties are synonymous to the errors incurred in the measurement process.
(a)
(i)
(ii)
(iii)
blunders
data not befitting the observed pattern of variation.
yield outliers.
(b) Systematic:
(i)
determinate, assignable and causes a consistent effect.
(ii) causes recognizable difference between the mean and an acceptable value or the true value where it is
known.
(iii) affect the accuracy (trueness) of the measurement. Cannot be revealed by replication.
(iv) minimizable/reducible if identified.
(v) comes from instrumental drifts/shifts, method bias and bias due to personal performance/ judgment.
(vi) effect can be constant (independent of sample size) or proportional (proportional to sample size).
Where a true or accepted value (certified value) or mean value of a large sample size is available, accuracy can be
expressed as the:
(i)
the absolute error, E x
i
(ii)
% relative error,
RE
xi
100%
Calculation of the actual error (bias) is only possible if the true value,, is known.
(i)
(ii)
(iii)
(b)
Random:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
Distribution of the deviations about the mean, , (sample) or the true value, , (population) take a Gaussian
distribution.
The Gaussian curve (shown below), also called the normal error curve has a distribution equation:
( x ) 2
2 2
(i)
sx
x
i 1
i 1
n 1
N = n -1 is degree of freedom.
Variance = s2x in the square of the standard deviation and is a positive quantity.
sx and s2x values are expressions of precision.
low values of sx, and sx2 implies high precision and vice versa.
The precision of the means (averaged sets of data) can be expressed as the mean standard deviation sm (also called
standard error or standard deviation of the mean).
sm
the sample standard deviation, sx, (a good approximation of (n > 30) is given by:
N
(ii)
s
n
Pooling the standard deviation for k data sets, each having n1; n2..nk replicates.
na
s pld
nz
j 1
z 1
( xi - x1 ) 2 nb 1( x j - x2 ) 2 ......... nz -1( xz - xz ) 2
na -1
i 1
( na nb ....n z ) - N
Corresponding estimated standard error, SE, sm about pooled data would be:
SE =
Properties of the Normal error curve.
(i)
(ii)
(iii)
(iv)
s pld
1 1
1
+ +..
n1 n 2 nk
68% of the means of the grouped data are within (/N) < < (/N),
95.5% of the means of the grouped data are within (2N) < < (2N) and
99.7 of the means of the grouped data are within (3N) < < (3N) of the
error curve, respectively.
This becomes the statistical basis for controlling random errors and improving the precision in routine analysis.
Example 1: Sample mean and standard deviation and the standard error.
1 (n=3)
2 (n=3)
3 (n=3)
4(n=3)
5 (n=3)
1.752
1.762
1.760
1.759
1.758
1.757
1.766
1.762
1.756
1.760
1.761
1.753
1.768
1.764
1.762
Three samples of voltaic cells were drawn out on an hourly basis from a production line and their weights recorded.
(i)
Calculate the mean production weight/mass, the standard deviation and the variance over the 5 h production period.
(ii)
Calculate the standard error (absolute uncertainty) in the mean weight of the voltaic cells. Use your scientific calculator
(in the Stats mode) to input the data.
(iii)
Ans:
If the targeted weight was 1.758 g, calculate the % relative standard deviation of weights from the targeted
production weight.
(i)
(ii)
(iii)
Thus,
= (1.760 0.003) g.
Do this on your own.
Digits that are certainly known in a number (or measurement value), including its estimated and uncertain digit
when the number is expressed in its standard form.
(i)
12.00 cm, 4 s.f.
12.0 cm is certain. The 2nd zero is uncertain, i.e. scales can measure accurately to only 0.01 cm.
(iii)
If 120 mm is reported as 1.2 x 102 mm, the result has 2 s.f., i.e. 1 mm is accurately recorded, the 0.2 is
uncertain.
If 120 mm is presented as 1.20 x 102 mm, the result has 3 s.f. instrument can measure accurately upto
0.1 mm.
Thus, 120 mm (non-standard form) is an ambiguous record of the measurement.
The number of s.f. assured in a number gives an idea of the level of precision in the measurement of that value.
Examples of operations and how the associated errors are combined are shown in the Table below.
Case
operation
Propagated error
z=xy
z x (y) 2
(2)
z = c(xy )
c= constant
2
2
z x y
z x y
(3)
z = c(y/x)
c= constant
2
2
z x y
z x y
(1)
(4)
(5)
z = cxa
c= constant
z x
a
z x
z = cxayb
2
2
z x y
a b
z x y
a,b,c= constants
(6)
z = log x
(7)
z = antilog x
x
z 0.434
x
z
2.303(x)
z
Note
x = xi - x = the measurement deviation.
For addition and subtraction operation: add the variance of the data.
For multiplication and division: add the square of relative deviations.
For a function of x and y, f(x,y): add the squares of product of the relative deviations of each variable and its exponent.
o
o
o
o
Worked example 2:
An aliquot of 25.00 ( 0.02) mL of a 53.4 (0.4)%, (wt/wt)} aqueous solution of NaOH with a measured density of
1.52 (0.01) g/mL is diluted to 2L (5 mL) with distilled water.
(a) Calculate the molar concentration of the dilute solution.
(b) Calculate the uncertainty in the concentration of the dilute solution.
Ans:
(a)
(b) Since C
= (v/v)2 + (/)2 + (wt/wt)2 + (V/V)2 (N.B. cases 2 & 3): add the square of the relative errors).
= (0.02/25.00)2 + (0.01/1.52) 2 + (0.004/0.534)2 + (0.005 L/2 L)2
(C/C)
= 0.0103
% relative error = (100C/C) = 1%.
Absolute error = 0.0103 x 0.2536 mol dm-3
= 0.003 mol dm-3
(C/C)2
Selection of a significant test is based on an appropriate sample distribution e.g. students t, Q or F-distributions.
Formulation of the null hypothesis, Ho and an alternative hypothesis, Ha.
Selection of the significance level.
Comparison of the test statistics (calculated value of the distribution) and the critical values (tabled values according to
(v)
Rejection of the null hypothesis, Ho or else one adopts a no evidence standpoint view.
sample size).
Student's t-distribution:
Properties:
Populations (from which the samples are drawn) are assumed to be normally distributed. Any deviations are due to
only random errors.
-applicable to a limited number of replicated measurements (finite sample sizes).
-mean,
The statistical distribution parameter, t, for a population with a true value of , where N replicated measurements have
been taken is given by:
and variance, sx2 of the measurements are calculated using a finite data, sample size = N.
Sx
Confidence interval: the range within which the true value for the data will lie at a specified level of confidence.
From eqn. 1, Confidence interval of :
t crt s x
2
tcrt values are listed in Statistical Tables at a specified confidence level (CL) and the degree of freedom, = N-1.
Example 3
The following results (as w/w% by mass) were obtained from the analysis of a standard alloy sample which
contained 57.85% Cr,
57.88;
58.00;
57.61;
57.80;
57.56; 57.61; 57.51; 57.77; 57.40 & 57.67.
(a)
(b)
(c)
Calculate the (i) mean (ii) standard deviation and (iii) variance.
95% confidence interval for the results.
Is the method measuring accurately at 95% confidence level? Show your working.
Ans.
(a)(i)
Mean,
x
N
(ii)
standard deviation,
sx
i 1
n 1
(iii)
(b)
x 0.18
,
57.68 2.2610
{tcrt(95%) = 2.26, = 9}
= 57.680.13%.
Thus, we are 95% certain the true value lies within the interval (CL) 57.55% - 57.81%.
*Repeat the same calculation at 99% confidence level.
c)
Note that true value (57.85%) is not included within the confidence interval.
The method is not accurate due to some systematic errors. Later on, you shall compare this approach with
the students t-test. (presented in Example 4 below).
Exercise 1
A vendor is keen on making a beverage containing a vitamin concentration of about 100 g/kg. The production
precision of the beverage is known previously to be 8 g/kg at the specified concentration level. He does some
clever calculations and decided to blend at least 10 samples to meet the Food Regulatory Authoritys requirement
specified at the 95% confidence level. Calculate the concentration range specified by the Regulatory Body.
Ans.
(b)
case 1:
same).
If and
are replaced by
texp x1 x2
test statistics:
n
sx .
level (CL).
tcrt ( = n-1) values can be quoted at CL of usually 90%, 95% and 99%.
x1
x2
At 95% CL, rejecting Ho when it is right or correct has a statistical risk of no more than 5%. The
probable risk of 0.05 is called the significance of the test sometimes quoted as P < 0.05).
Example 4:
4a) Apply a t-test to answer Q 3c in Example 3 above.
Ans: to Q3c
x1 = ( x2
x1 x2
are due to random errors. or else Ha: the two means are not same.
Test the hypothesis, by calculating texp:
test statistics: t exp
57.85 57.68
10
0.18
2.29
Compare: texp. (= 2.29) > tcrt(0.05,9) (= 2.26) at the 95% level, so we can be 95% certain that the method is
not measuring accurately.
*Repeat the calculation at 99% confidence level.
4b) Suppose the standard deviation of measuring the % Cr in the alloy (Example 3) is known from experience to be
0.12%. To check on the accuracy of the method, a reference material is measured three times giving an average
of 57.94%. Is the method measuring accurately at 95% confidence level?
Population standard deviation, = 0.12% (n = ); = 57.85%; Nreplicated = 3
test statistics:
texp xi
3
0.12
Conclusion: There is no evidence of inaccuracy in the measurements by the method at 95% based on
previous experience on the performance of the method.
Case 2:
Two means,
First apply an F -test to establish that sB and sA (i) are significantly different or (ii) not significantly different at a
given level of confidence e.g. 95%., see F test Example 6
If sB and sA are not significantly different, we pool the standard deviation for the two data sets.
x A and x B
different from each other, the pooled and estimated standard deviation, spld,
s pld
( N A 1) s 2 A ( N B 1) s 2 B
( N A - 1) ( N B - 1)
test statistics: t x A xB
exp
s pld
N A N B . 4
N A NB
texp > tcrt (0.05, = NA + NB 2), then reject Ho and conclude that
xA
xB
confidence level.
Example 5
The content of Cr in the alloy was re-analyzed by a gravimetric method and a mean of 57.89% and standard
deviation of 0.33% was calculated from 4 determinations. Is the performance (in terms of accuracy and precision) of
the gravimetric method any better than the previous method at 95%?
Summary of the two methods performance parameters.
Routine
sx
10
4
57.68
57.89
0.18%
0.33%
gravimetric
HO:
x (routine) = x (gravimetric)
First, do an F- test to establish whether the two precisions are statistically different.
Assuming no significant difference between their precisions, the pooled standard deviation, spld., (eqn. 4):
s pld
( N A 1) s 2 A ( N B 1) s 2 B
( N A - 1) ( N B - 1)
9 x0.182 3x0.332
(10 1) (4 1)
= 0.226
t exp
57.89 57.68
0.226
10 x 4
10 4
= 1.563
Since texp. (= 1.56) < tcrt { = 12; CL= 95%} = 2.18), we cannot be 95% certain that the performances of two
methods are different. Thus, there is no statistical evidence that the gravimetric method is better than the other
method. If anything, its only random errors.
Case 3 Paired t test
Is used to compare two data sets (generated from several but unique samples (A, B, C) measured
under two sets of conditions:
The different conditions can be in the form of:
i)
two methods where one is a candidate method the other a standard method,
ii)
or two analysts
iii)
or two laboratories.
A, B, C. samples are unique in terms of concentration levels or identity e.g. soil, oil, air.
You cant use the simple cases 1 and 2 because the data is paired-up.
Calculate the differences (maintaining the sign on each difference) in each pair of results; calculate the
mean of the differences and the standard deviation of the differences.
o
Null hypothesis: H0: d = 0 i.e. there are no significance differences in all the paired results.
Or else Ha: d 0 i.e. Any differences are due to random errors. or else Ha: the means from the
paired-up data are non-zero.
texp d 0
o
N
sx
Compare: texp. with tcrt(0.0, v) , and reject or retain the null hypothesis.
The F distribution
Used to compare the precision of measurements (usually prior to comparing their means).
The distribution parameter for variance is Fcrt, and is calculated from the ratio (sA2/sB2) of the sample variances of two
sets of experimental measurements.
Fcrt values are listed in F-tables (at the intersection of their respective no. of degrees of freedom; 1 = n1-1 and 2 =
To calculate Fexp, the variance of the higher precision (smaller sx2 value) appears in the denominator.
n2-1).
F-test
Ho: sA2 = sB2 i.e. (sA2/sB2) = 1. The variance are the same i.e. their ratio = 1 The actual differences in the
spread of the measurements about the means (precision) or variances are due to random errors only.
Or else Ha: sA2 sB2
Fexp. = (sA2/sB2), (1; 2 = N1-1; N2-1) at the stated CL, is calculated such that ratio > 1.
Fexp > Fcrt, Reject Ho, thus, the precision in measurements of data set A is statistically different from that of B.
Example 6
Was the assumption on the precisions of the two methods in worked Example 5 above valid in the first place?
Null hypothesis, Ho: s2routine = s2gravimetric (no difference in the precision of the methods) Or else: Ha: sA2 sB2
Fexp, = (s2gravimetric/s2routine) = (0.332/0.182) = 3.36
Fexp (= 3.36) < Fcrt, {(1; 2 = 4; 9 at 95%)} = 3.63.
Thus, there is no evidence at 95% that the precisions of the two methods are different. The assumption to pool the two
standard deviations was valid.
Q-test/Dixon test:
One or two values may differ considerably from the rest of replicates set of measurements.
Can the suspicious value(s) be excluded from any subsequent calculations (e.g. of the mean value, x and sx)?
o A Q-test is performed to confirm whether such a suspect value is an outlier.
o An outlier is a datum (observed within a replicated data set) which is conspicuously different from the rest of the
data in terms of it distribution pattern. (It is usually caused by gross errors or blunders. It can also be declared
Null hypothesis, Ho, for Q-test: The suspect value is part of the set of data i.e."There is no difference between the
suspect value and the rest of the values. (Any differences must be attributed to random errors).
Calculate (Qexp):
Qexp
( x suspect xnearest )
xmax x min
..5
Compare Qexp with Qcrt (for the number of measurements taken, N) at a specified confidence level (95%) from the
tables.
If Qexp > Qcrit, reject HO, treat the suspect as an outlier; exclude it from subsequent calculations at the stated CL.
Otherwise the suspect value is retained on the basis of lack of evidence (proving existence of such a difference).
Treat the Q-test with caution especially when only few measurements.
Example 7
The density, /(g mL-1) of a certain metal was measured 6 times; the results were ranked in the following order:
/(g mL-1): 2.19; 2.23; 2.42; 2.68 and 4.36.
4.36 appears to be conspicuously bigger than the rest.
Calculate Qexp (eqn. 5) = (4.36 2.68)/(4.36 - 2.19) = 0.774 > Qcrt(0.05, 6) (= 0.63).
At 95% CL and N = 6, reject the Null Hypothesis and treat 4.36 as an outlier.
Note: mean, x = 2.77 and median = 2.42 and x (excluding the suspect) = 2.38.
The median is not affected by the inclusion of an outlier in the data set, and is a better estimator of the centrality
than x for data that include an outlier.