MSA - Case Study MU

MEASUREMENT OF UNCERTAINTY
Common Parameters
● Mass
● Volume
● Formula Weight
● Purity of Reference Materials
1
Mass by Difference
1)Based on linearity:
● When Mass is measured by difference the uncertainties
due to calibration of weights and daily drift cancel out
● Uncertainty will be due to repeatability and the linearity of
the balance
● As the weight is taken by difference, both the linearity and
reproducibility values for Uncertainty have to be multiplied by
● For example weighing 2.002 g by difference using a
weighing dish of weight 55.2264g, for balance having linearity
0.15 mg and repeatability 0.05 mg the Uncertainty in weight
will be (linearity should be considered as rectangular)
U = Sqrt (2 x 0.052 + 2 x 0.0872) = 0.14 mg
2
2)Based on Calibration Uncertainty

If Uncertainty mentioned by the Calibration agency in the
calibration certificate used for Uncertainty calculation then
Uncertainty to be calculated as
Example : Accuracy of the balance 0.0002g

Resolution of the balance 0.0001g
Uncertainty from calibration certificate 0.0006g
Accuracy is rectangular hence Ua =0.0002/√3 = 0.0001154g
Resolution is rectangular hence Ur= 0.0001/ √3 = 0.0000577g
Uncertainty from calibration certificate =0.0006 k factor =2

hence Uc = 0.0006/2 =0.0003g
17
Then Uncertainty is √ (Ua)2 + (Ur)2 +(Uc )2
Then Uncertainty is √(0.0001154)2 + (0.0000577)2 + (0.0003)2 =

0.00033 g
If mass is taken by difference then Uncertainty is multiplied by

2 times
17
Uncertainty in formula weight:
Standard Total Weight = Uncertainty = Standard

Uncertainty (IUPAC No. of atoms x Uncertainty x No. of
Table) ATWT atoms
C8 0.00046(0.0008/sq3) 12.011 x 8 = 0.00046

96.088 X 8 = 0.00368
H5 0.00004(0.00007/ 1.00794 x 5 = 0.00004 x 5 = 0.0002

sq3) 5.0397
O4 0.00017(0.0003/sq3) 15.9994 x 4 = 0.00017 x 4 = 0.00068

63.9976
K 0.000058(0.0001/ 39.083 x 1 = 0.000058 x 1 =

sq3) 39.083 0.000058
5
Molecular weight of KHP = 96.088 + 5.0397 + 63.9976 +39.0983 =

204.2236 g/mol
Uncertainty with formula weight =Sqrt (0.003682+ 0.0002 2+ 0.000682 +

0.0000582) = 0.0047g / mol
6
To calculate Uncertainty associated with volume
a.Burette
Burette details : 25 ml burette, 0.1 ml graduation
Uncertainty Value Distribution Uncertainty
Component
Calibration ± 0.05 Triangular 0.05/sqrt6=0.02
accuracy
Repeatability 0.0013
σ/√6
Temperature 25 x 3 x 2.1 x 10-4 Rectangular 0.0154/
Variation = 0.0154 sqrt3=0.0089
End Point(1/2 0.1 / 2 = 0.05 Rectangular 0.05 /sqrt3 =
length interval) 0.029
Combined Uncertainty = Sqrt(0.022+ 0.00132+ 0.00892 + 0.0292) = 0.034ml
Note : Temperature Variation is ±3 co-efficient of expansion of water is 2.1 x 10 -4 / deg

C. Hence formula for TV = Volume capacity x 2.1 x 10 -4 x 3
7
For Burette at Different Volume Uncertainty is calculated by

interpolation formula
Example 25ml Burette graduation 0.1ml Uncertainty at different volumes is as
below
Volume,ml Uncertainty ±,ml
5 0.006
10 0.011
15 0.017
20 0.023
25 0.029
for 7.6ml Uncertainty is calculated as
A5 0.006X
B7.4 Y
C10 0.011Z
Y=X+(Z-X)*(B-A)/(C-A)
0.006+((0.011-0.006)*(7.4-5))/(10-5)
For 7.4ml
Uncertainty
is 0.0084ml
8
To calculate Uncertainty associated with volume
a.Pipette
Pipette details : 5 ml pipette

Component
Calibration ± 0.015 triangular 0.015/sq6=
accuracy 0.00061
Repeatability 0.0004
σ√6
Temperature 5x 3 x 2.1 x 10-4 = rectangular 0.0032/Sq3
Variation 0.0032 =0.0018
Combined Uncertainty = Sqrt(0.000612+ + 0.00042 + 0.00182) = 0.017ml
Note : Temperature Variation is ±3 co-efficient of expansion of water is 2.1 x 10 -4 /

deg C. Hence formula for TV = Volume capacity x 2.1 x 10 -4 x 3
9
c. Volumetric Flask, 100 ml

Volumetric Flask details :

Component
Calibration ± 0.1 Triangular 0.1/sqrt6=0.041
accuracy
Repeatability σ√6 0.002
Temperature 100x 3 x 2.1 x 10-4 = Rectangular 0.064/sqrt3 =0.037

Variation 0.064
Combined Uncertainty = Sqrt (0.0412+ + 0.0022 + 0.0372) = 0.055ml
Note : Temperature Variation is ±3 co-efficient of expansion of water is 2.1 x 10 -4 / deg

C. Hence formula for TV = Volume capacity x 2.1 x 10 -4 x 3
10
Purity reference material :
Purity Uncertainty Distribution Standard

Uncertainty
a) 99.9 ± 0.1 Rectangular 0.1/sq3=0.058
b) 99.9min 100 max ± 0.1 Triangular 0.1/sq6=0.041
c) 99.9 ± 0.1,95% ± 0.1 Normal 0.1/2 = 0.05

confident level
11
CASE STUDY/EXAMPLES
(A) ESTIMATION OF UNCERTAINTY IN
VOLUMETRIC ANALYSIS
GRAVIMETRIC ANALYSIS
INSTRUMENTAL ANALYSIS
(B) UNCERTAINTY EVALUATION USING PRIOR

COLLABRATIVE AND VALIDATION DATA
12
VOLUMETRIC ANALYSIS
Uncertainty in Alkalinity estimation in water
Test method :IS 3025
Trial no 1 2 3 4 5 6
Volume of water taken,ml A 25 25 25 25 25 25
Normality of Hcl,N 0.04968 0.04968 0.04968 0.04968 0.04968 0.04968

Volume of Hcl
consumed ,ml,B 3.1 3.15 3.1 3 3.15 3.1
Alkalinity ,mg/ ltr as
CaC03=(BxNx50x1000)/A 307.5 312.41 307.45 298 312 307
Average value ,mg/l 307.45
Standard deviation σ 5.43

Standard deviation about
mean= σ/√n,n=6 2.22 Repeatability Type A Uncertainty is 2.22 UA
13
VOLUMETRIC ANALYSIS
Sources of Uncertainty
1)Due to Sample Volume,ml (Pipette)
2)Due to Volume of Hcl Consumed,ml (Burette Reading,ml)
3)Due to normality of Hcl
4)Due to molecular weight of CaCO3
5)Repeatability
14
VOLUMETRIC ANALYSIS
Fish Bone Diagram
15
VOLUMETRIC ANALYSIS
Fish Bone Diagram
16
VOLUMETRIC ANALYSIS
TYPE B Uncertainty
1)Due to pipette volume,ml
25ml pipette used, Class A Id number 40-2010-25-1
Uncertainty from record number CR-P-25 is 0.06ml k=2 Hence Uncertainty is
0.06/2=0.03ml Up
2)Due to Volume of Hcl Consumed Burette Reading,ml
Burette 25ml 0.1ml graduation Uncertainty from record number CR-B-25 for 3.1 ml
volume Uncertainty calculated by interpolation formula is 0.0037ml Ub
3)Normality of Hcl
Tno 1 2 3 4 5 6
Weight of
25.2 25.5 25.6 25.4 25.3 25.2
Na2CO3,mgW
Volume of Hclml,V 9.6 9.7 9.7 9.6 9.6 9.6
Normality=W,mg *p
0.04952 0.04960 0.04980 0.04992 0.04972 0.04953
/EqwtNa2co3 X V
Mean 0.04968
σ 0.000160
σ about n=6, p-purity of sodium
mean 6.55844E-05 = σ√(n) Carbonate -100%
17
VOLUMETRIC ANALYSIS
3)Uncertainty in normality of Hcl
a)Uncertainty due to weight
b)Uncertainty due to volume of Hcl
c)Uncertainty due to equivalent weight of Na2CO3
d)Repeatability
Calculation of Uncertainty in normality of Hcl

a)Uncertainty due to weight of Sodium Carbonate taken
Balance ABSFACT USED with details as below
Standard
Particulars Value Uncertainty Distribution
Accuracy ,g 0.0002 0.0002÷√3 Rectangular
Resolution ,g 0.0001 0.0001÷√3 Rectangular
Calibration uncertainty
,g 0.0006 0.0006÷2 Normal K=2
Hence Uncertainty due
to Mass Um √(0.0001154)2+(0.0000577)2+(0.0003)2
Hence Uncertainty due
to Mass Um,g 0.00033
18
VOLUMETRIC ANALYSIS
b)Uncertainty due to Volume of Hcl for Standardization
Burette 25ml 0.1ml graduation Uncertainty from record number CR-B-25 for 9.6 ml
volume Uncertainty calculated by interpolation formula is U v 0.0106ml
c)Uncertainty due to formula weight Of Sodium Carbonate
Atomic Uncertainty Standard
Formula weight , g IUPAC Uncertainty
Na2 2x22.9877 0.000002 2x0.0000115 0.023x10-4
C 1x12.01017 0.0008 1x0.0004618 4.6x10-4
O3 3x16.0003 0.0003 3x0.000173 5.1x10-4
NOTE IUPAC Uncertainty is Rectangular Hence uncertainty is divided by √3
Uncertainty in Sodium Carbonate molecular weight , g 6.868X10 -4
Total Molecular weight 105.9865 ,since equivalent weight is 1/2 molecular weight
Uncertainty in equivalent weight is 6.868X10-4/2 =3.43X10-4
Uncertainty in equivalent of Weight Sodium carbonate ,g is U E3.43X10-4
19
VOLUMETRIC ANALYSIS
d)Uncertainty due to purity of standard (Sodium Carbonate)

From NIST Traceable Certificate Number k-02 purity is mentioned as 100 ± 0.05% k
factor =2
Hence uncertainty in purity is 0.05/2 (Normal Distribution) =0.025%
Hence uncertainty for normality is calculated as
Relative
Standard standard
uncertainty uncertainty
Parameter Value V U U/V
Weight,mg 25.37 0.33 0.01301
Volume Of Hcl for
Standardisation,ml 9.63 0.0106 0.00110
Eqwt. of Sodium
carbonate,g 52.99325 0.000343 0.000006
Purity of std 100 0.025 0.00025
Repeatability Sd
abt mean 0.04968 0.0000655 0.00132
Uncertainty in normality of Hcl =Normality of Hcl (0.04968)X
√(0.01301)2+(0.00110)2+(0.000006)2+ (0.00025)2+(0.00132)2= Un= 0.00065
20
VOLUMETRIC ANALYSIS
4)Uncertainty in Molecular weight of CaCO3 already calculated 0.0024 since
equivalent weight is used Equivalent is Molecular weight ÷2 so uncertainty is also
÷2 hence uncertainty is 0.0024÷2 =0.0012gUe
Final calculation of uncertainty in Alkalinity Estimation is
Standard Relative std
uncertainty uncertainty,
Parameter value V U U/V TYPE
Sample
volume,ml(Pipette) 25 0.03 0.001200 Type B
Volume of Hcl
consumed ,burette
reading,ml 3.1 0.0155 0.005000 Type B
Normality of Hcl,N 0.04968 0.00065 0.013084 Type B
Equivalent weight Of
CaCO3,g 50.0004 0.0012 0.000024 Type B
Repeatability (as Sd
about mean),mg/ltr 307.45 2.21 0.007221 Type A
Uncertainty in Alkalinity U = Mean Alkalinity value(307.45) X
√(0.001200)2+(0.005)2+(0.013084)2+ (0.000024)2+(0.007221)2=U=4.86
21
VOLUMETRIC ANALYSIS
Effective Degrees of Freedom
(U) 4
------------------------------------------------------------------------------------------------------------
(UA) 4/5 + (Up) 4/∞+ (Ub) 4/∞+ (Un) 4/∞+ (Ue) 4/∞
=122
SO COVERAGE FACTOR =2 @95%Confidence Level
Therefore Uncertainty in Alkalinity Estimation is

307.45±2*4.86 = 307.45 ± 9.72 mg/ ltr
%Uncertainty is 3.2
22
Ash content in Chilly powder

Test method:ASTA METHOD
Tno 1 2 3 4 5 6
Sample Weight ,g 2.2119 2.0826 2.1212 2.0602 2.0292 2.0144
Crucible + Residue
30.4582 23.2393 23.2468 30.183 29.2323 31.131
Weight ,g
30.2946 23.0846 23.0896 30.032 29.0821 30.9816
Crucible Weight , g
Residue Weight , g 0.1636 0.1547 0.1572 0.152 0.1502 0.1494
Ash%=
Residue weightX100/ 7.40 7.43 7.41 7.38 7.40 7.42
Sample weight
Average Ash% 7.41
Standard Deviation σ 0.0187
σ about mean= σ/√6 0.00763 Type A Uncertainty UA
23
Sources of Uncertainty
1)Due to Sample weight
2)Due to Residue weight
3)Due to Temperature Tolerance of ±20 degree centigrade
4)Due to Muffle Furnace Temperature Tolerance
24
25
Calculation of Uncertainty Type B

1)Sample weight Balance ABSFCT used with details as below
Standard
Particulars Value uncertainity Distribution
Accuracy , g 0.0002 0.0002÷√3 Rectangular
Resolution, g 0.0001 0.0001÷√3 Rectangular
Calibration uncertainty , g 0.0006 0.0006÷2 Normal K=2
Hence uncertainty due to Mass ,g
√(0.0001154)2+(0.0000577)2+(0.0003)2 = 0.00033 UM
Since Sample Weight is taken by taring hence uncertainty is 0.00033, g
2)Residue weight
Same Balance is used uncertainty as above for Balance is 0.00033,g but
Residue weight is
taken by difference(Final weight- Initial weight)hence uncertainty is multiplied
2 times
Therefore uncertainty in residue weight is 0.00066 , g UR
26
3)Due to Temperature Tolerance of ±20 degree centigrade
Procedure specifies ash to be done at 600±20 degree centigrade uncertainity due to
temperature difference is defined as below. To find the uncertainity due to
temperature difference two sets of results done one at 580 degree centigrade and
one at 620 degree centigrade
Ash at 580 oC Ash at 620oC
Tno 1 2 Tno 1 2
Sample Weight ,g 2.2119 2.0004 Sample Weight ,g 2.0602 2.0001
Crucible +
Cruicible + Residue Weight ,g 30.4582 32.4590 Residue Weight ,g 30.1838 30.1768
Cruicible Weight,g 30.2946 30.3116 Crucible Weight ,g 30.0318 30.0297
Residue Weight,g 0.1636 0.1474 Residue Weight ,g 0.152 0.1472
Ash%= Residue
Ash%= Residue WeightX100/ WeightX100/
Sample Weight 7.40 7.37 Sample Weight 7.38 7.36
Ash, % 7.385 Ash, % 7.375
27
So difference of 20 degree centigrade change is 1)0.025% (2)0.035% SINCE
0.035% is Maximum it is taken for calculation
Temperature range for Ash is 580-620 degree centigrade i.e., 40 degree
difference therefore 0.035% is multiplied by 2 i.e.,0.07%
0.07% is divided by square root of 3 because this change is rectangular
distribution
Therefore uncertainty due to temperature tolerance is 0.07%÷√3 =0.040% UT
4)Muffle furnace Temperature Tolerance
Details of the muffle furnace is as below
Particulars Value Standard uncertainity Distribution
Accuracy,oC 5 5÷√3=2.8868 Rectangular
Resolution,oC 1 1÷√3=0.5774 Rectangular
Calibration uncertainity,oC 1.3 1.3÷2=0.65 Normal K=2
Hence uncertainty in muffle furnace temperature is √2.8872+ 0.5772+0.652 =
3.01oC
So ±3oC uncertainty in muffle furnace temperature changes the ash content by
0.035*3/20
i.e., 0.00525 also it is rectangular hence 0.00525÷√3 is uncertainty= 0.0030 % UF
28
Calculation of Uncertainty
Value Standard Relative Standard
Parameter V Uncertainty U Uncertainty, U/V
Sample Weight , g 2.0866 0.00033 0.00016
Residue Weight ,g 0.1546 0.00066 0.00427
Temperature difference
o
C(Change in Ash value %) 7.41 0.04 0.00540
Muffle Furnace Temperature

Tolerance o C(Change in Ash
Value%) 7.41 0.003 0.00040
Repeatability as σ about
mean 7.41 0.00763 0.00103
Uncertainty in Ash content = Mean Ash
Value(7.41%)*√0.001582+0.004272+0.005402+0.000402+0.001032 = 0.052% U
Effective Degrees of Freedom 10479 ≈ ∞
So Coverage Factor is 2.0 Hence Expanded Uncertainty in Ash content is
7.41 ± 2*0.052 =7.41 ± 0.104 % Uncertainity is ±1.4
29
Effective Degrees of Freedom
(U) 4
------------------------------------------------------------------------------------------------------------
(UA) 4/5 + (UM) 4/∞+ (UR) 4/∞+ (UT) 4/∞+ (UF) 4/ ∞
Effective Degrees of Freedom 10479 ≈ ∞

So Coverage Factor is 2.0 Hence Expanded Uncertainty in Ash content is
7.41 ± 2*0.052 =7.41 ± 0.104 % Uncertainity is ±1.4
30
Uncertainty in Benzoic Acid Estimation By HPLC

Trial no 1 2 3 4 5 6
Sample Weight , g W 2.1126 2.0826 2.0139 2.0213 2.0216 2.0214
Volume made up , ml A 100 100 100 100 100 100

Area from HPLC 32368.7 31570.2 31148.7 30888.8 30696.8 30333
Conc. from graph C,ppm 11.32 11.04 10.89 10.8 10.73 10.6
Recovery Factor R 0.991 0.991 0.991 0.991 0.991 0.991
Benzoic acid ppm,=
(C X A)/R*V 540.7 534.9 545.7 539.2 535.6 529.2
Mean Benzoic Acid
Content, ppm 537.5
Standard Deviation Type A Uncertainty ,Uncertainty due to
about mean =σ /√6 2.31 repeatability
31
Source of Uncertainty
1)Due to repeatability
2)Due to sample Weight
3)Due to volume made up
Due to concentration read from calibration graph which consists of

two parts as below
4)Due to preparation of calibration Standard
5)Due to generation of calibration curve

6)Uncertainty in Recovery Factor
32
33
1)Uncertainty due to Sample Weight ,Balance ABSFCT Uncertainty , g 0.00033
2)Uncertainty due to volume made up 100ml volumetric flask Class A id number

A-EJ485319 100 volumetric flask ,Uncertainty,ml 0.055
3)Uncertainty Due to preparation of Calibration Standard
From 1001 ppm STOCK Calibration standard is prepared by Pipetting

0.05,0.1,0.2,0.3,0.4,0.5 ml into 10ml volumetric flask and made up to 10ml to get
5,10,20,30,40,50 ppm Calibration Standards uncertainty involved as below
For 1001ppm Uncertainty Mentioned in COA of NIST is ±3 k factor is 2 hence

Uncertainty is 3÷2 =1.5ppm
34
3. Uncertainty in Calibration Standard
Uncertainty
for
Conc of Calibration
Uncertainty Calibration
Concentration from Volume Uncertainty Volume Uncertainty
std ,ppm
of Stock Certificate of pipette, for pipette, made up for 10 ml standard (Us)= S*
Standard ,ppm NIST ml ml ml, flask , ppm √(b/a)2+
a b c d e f (S) (d/c)2+(f/e)2
1001 1.50 0.05 0.00005 10 0.03 5.00 0.02
1001 1.50 0.1 0.0001 10 0.03 10.00 0.03
1001 1.50 0.2 0.0001 10 0.03 20.00 0.07
1001 1.50 0.3 0.0001 10 0.03 30.00 0.10
1001 1.50 0.4 0.0001 10 0.03 40.00 0.13
1001 1.50 0.5 0.0001 10 0.03 50.00 0.17
35
4) Due to Generation of Calibration curve
For this statistical procedure adopted as below
Conc, ppm
X Area Y X2 Y2 XY
0 0 0 0 0
5 14498.5 25 210206502 72492.5
10 30227.4 100 913695711 302274
20 56110.4 400 3.148E+09 1122208
30 84371.7 900 7.119E+09 2531151
40 112994.3 1600 1.277E+10 4519772
50 143092 2500 2.048E+10 7154600
36
∑X 155
(∑ X)2 24025 Sxx= ∑x2- {(∑x)2/n} 2092.8571
∑Y 441294.3 SYY= ∑y2- {(∑y)2/n} 1.681E+10
(∑ Y)2 1.947E+11 Sxy= ∑xy- {∑x* ∑y}/n} 5930980.9
∑ X2 5525 (m)slope =Sxy/Sxx=2833.92
∑ Y2 4.463E+10 Sr σ about regression√(SYY-m2Sxx)/n-2 = 1086.36
∑ XY 15702498
∑ X ∑ Y 68400617
Sc std deviation about CALIBRATION CURVE Sc
(Sr/m)* [√1/M+1/n+ {(Sample Area-Median y)2/m2Sxx}]
Sample Area 32368.7 m=2833.92, Sr=1086.36,
Median y =∑Y/n n=number of calibration points =7
63042.043
M=Instrument replicates =1
n=7 ,number of Calibration
Points Sample Area =31167.7 , Median =63042.043
SC uncertainty read from calibration curve USc 0.281ppm
37
5.Uncertainty due to Recovery Factor

Six trials for recovery were done and details as below
Tno Recovery
1 0.989
2 0.991
3 0.995
4 0.994
5 0.99
6 0.987
Mean 0.991
σ 0.00303315
Uncertainty in recovery factor σ / √6 =0.001239
38
Relative standard
Standard Uncertainty
Parameter Value V Uncertainty U U/V
Repeatability 537.5 2.31 0.00430
Sample Weight ,g 2.0456 0.00033 0.00016
Made up volume,ml 100 0.055 0.00055
Due to std,ppm
Std1 5.00 0.017 0.00350
Std2 10.00 0.035 0.00350
Std3 20.00 0.068 0.00339
Std4 30.00 0.101 0.00337
Std5 40.00 0.135 0.00336
std6 50.00 0.168 0.00336
Recovery Factor
Uncertainty 99.10 0.0012 0.00125
Due concentration
from calibration curve, 10.89 0.282 0.02588
ppm
39
UNCERTAINITY IN Benzoic Acid Estimation =

Conc. Of Benzoic acid (537.5)
*√0.00432+0.000162+0.000552+0.00352+0.00352+0.003
392+0.003372+0.003362+ 0.001252+0.0025882 =
14.8ppm
Effective Degrees of Freedom =8847,≈ ∞
Therefore Coverage Factor is 2 Hence Uncertainty in

Benzoic acid estimation is 537.5 ± 2*14.8 =
537.5 ± 29.6 ppm %Uncertainty is 5.5
40
Uncertainty in Riboflavin estimation by HPLC
Trial no 1 2 3 4 5 6
Sample Weight,g W 2.1126 2.0826 2.0139 2.0213 2.0216 2.0214
Volume made up,ml V 100 100 100 100 100 100
Area from HPLC for sample A2 32368 31570.2 31148.7 30888.8 30696.8 30333
Standard Concentration, ppm S 10.41 10.41 10.41 10.41 10.41 10.41

Area from HPLC for standard A1 32351 32351 32351 32351 32351 32351
Recovery Factor R 0.991 0.991 0.991 0.991 0.991 0.991
Benzoic acid ppm,=
(S*V *A2)/R*W*A1 497.5 492.2 502.2 496.2 493.0 487.3
Mean Benzoic Acid content,ppm 494.7
Standard Deviation about mean
=σ /√6 2.09 Type A
Uncertainty due to repeatability =2.09 Degrees Of Freedom =5
41
Source of uncertainty
1)Due to repeatability
2)Due to sample Weight
3)Due to volume made up
4)Due to preparation of Standard
5)Due to Sample Area
6)Due to Standard Area
7)Due to recovery factor
42
43
1)Uncertainty due to Sample Weight ,Balance ABSFCT Uncertainty ,g 0.00033

2)Uncertainty due to volume made up 100ml volumetric flask Class A dumber A-
EJ485319100 volumetric flask ,Uncertainty,ml 0.055
3)Uncertainty Due to preparation of calibration standard
10.41 mg Standard taken and made up to 1000ml
Standard Concentration = Weight of standard ,mg X Volume Made up ,ml *p/ 1000
p-purity from COA is 100% with uncertainty in COA ±0.05 %K FACTOR =2 hence
uncertainty is 0.025%
Therefore uncertainty in standard preparation is
Uncertainty in
Balance Standard
Uncertainty Volume Uncertainty Purity Uncertainty Concentration
Weight , mg ,mg made up of Flask ,ml % in Purity,% is C*√(b/a)2+
a b , ml c d e f (d/c)2+ (e/f)2
10.14 0.033 1000 0.055 100 0.025 0.6
C- Concentration of working standard =10.14 ppm

44
4)Uncertainty due to Standard Area 5)Uncertainty due to Sample Area
Same 10.14 ppm Standard Solution Same Sample solution injected for 6
injected for 6 times times
Tno Area Tno Area
1 32362 1 32378
2 32352 2 32368
3 32348 3 32364
4 32368
4 32346
5 32344 5 32388
6 32354 6 32342
Mean 32351 Mean 32368
σ 6.54 σ 15.44
σ/√6 2.67 σ/√6 6.30
45
5.Uncertainty due to Recovery Factor

Six trials for recovery were done and details as below
Tno Recovery
1 0.989
2 0.991
3 0.995
4 0.994
5 0.99
6 0.987
Mean 0.991
σ 0.00303315
Uncertainty in recovery factor σ / √6 =0.001239
46
Evaluation of Total Combined Uncertainity

Relative standard
Standard uncertainty
Parameter Value V Uncertainty U U/V
Repeatability 497.5 2.09 0.00421
Sample Weight ,g 2.0456 0.00033 0.00016
Made up volume , ml 100 0.055 0.00055
Uncertainty in Standard
Concentration, ppm 10.14 0.6 0.05966
Uncertainty in Standard
Area 32351 2.67 0.00008
Uncertainty in Sample
Area 32363 6.3 0.00019
Recovery Factor
Uncertainty 0.991 0.001239 0.00125
UNCERTAINITY IN Riboflavin Estimation = Conc. Of Riboflavin (497.5)

*√0.004212+0.000162+0.000552+0.059662+0.000082+0.000192+0.001252 = 34.41ppm
47
Effective degrees of freedom 366116 ≈∞

For Expanded Uncertainity Coverage factor k is 2
So Expanded uncertainty in Riboflavin estimation is

497.5 ± 2* 34.41 = 497.5 ± 68.8ppm %Uncertainty is 13.8
48
Evaluation of Uncertainty-Using Prior Collaborative /Validation Data

Case Study of Dietary Fiber Analysis Method 985.29 AOAC
Method Performance Data
Number Of Laboratories 9
Average Dietary Fiber % 23.25
Repeatability Sr σ 0.74
Reproducibility SR σ 0.97
%RSD Sr 3.03
%RSD SR 3.95
Laboratory Data
Tno %Dietary Fiber
1 24.54
2 24
3 25.23
4 24.98
5 23.9
Mean 24.53
Repeatability SL σ 0.59
49
Applying F test for SL and Sr

F= Sr2/SL2 0.742/0.592 F= 1.57
F critical for 9-1 = 8 degrees of freedom for S r
F critical for 5-1 = 4 degrees of freedom for S L
Therefore F critical is 8.98

Since F is less than F critical (1.57 Less than 8.98) Value Precision is Under Control
and Uncertainty is 2*Sr = 2*0.74 =1.48%
Therefore Uncertainty in Dietary Fiber Estimation Is 24.53 ± 1.48%

%Uncertainty is 6.03
50
Measurement Uncertainty
51
The Instrument under calibration is a micrometer of 0 –25 mm range with a slip gauge of
25 mm on nominal size
The Detailed specification of the slip gauge are as follows
Range = 25 mm, Calibrated value = 25.00010 ±0.00008 mm

Standard reference temperature : 20° C, Actual Temperature : 23°C
52
Five readings are taken and the deviation from the nominal value is as
follows
Observation Deviations from nominal value
numbers mm
1 0.001
2 0.000
3 0.001
4 0.000
5 0.001
Standard uncertainty due to the flatness of micrometer faces say (1½ fringe) = 0.5 m
Standard uncertainty due to the parallel ness of micrometer faces say (1½ fringe) = 0.5
m
Standard thermal expansion coefficient of the slip gauge is 11.5 X 10-6/ ° C
Mathematical model : Y = Xstd + X
53
Mean deviation : x/ n = 0.003/5 = 0.0006 mm x
Standard Deviation : s (x) = {1/(n-1)  (xj –x) 2}

=  1/4 (12 x 10 –7) =  3 x 10 –7
= 5.47 x 10 –7
mm 
Standard Error of the mean : S (x) =  s2 (t) / n =(5.47 x 10 –7)

/  5 mm
Standard Uncertainty u(x) =2.446 x 10 –4

mm = 0.2446 m u(x
)
54
The Uncertainty quoted in the gauge block calibration certificate is

considered to be Type B uncertainty
Standard uncertainty due to the flatness of micrometer faces say
(1½ fringe) = 0.5 m
u1
Standard uncertainty due to the parallel ness of micrometer faces say
(1½ fringe) = 0.5 m u2
Standard thermal expansion coefficient of the slip gauge is 11.5 X 10-6/ ° C
Standard uncertainty due to difference in thermal expansion coefficient of
slip gauge and micrometer ( app 20 %)
= (25X3X11.5X10-6 X0.2) = 0.0001725 mm = 0.1725 m u3
Standard uncertainty due to standard used for calibration= 0.08 m u4
55
Sources of Estimates (Xi) Probability Standard Uncertainty

Distribution Contribution
Uncertainty m Uncertainty
Type A or B m
Flatness 0.5 Type B U (X1) /3 0.288
Parallelism 0.5 Type B U (X1) /3 0.288
Thermal Expansion 0.1725 U (X1) /3
Type B 0.099
Calibration 0.08 Type B U (X1) /3 0.046
Repeatability () 0.547 Type A U (XN)/5 0.2446
Uc= 0.4875
 (u12+u22+U32 u42+U52)
Expanded K=2
uncertainty
2x 0.4875 = 0.98
Reporting of results : The Value at 25 mm is 25.00010 ± 0.00098

mm(With a coverage factor k =2 for confidence level of 95.4 %)
56
A digital thermometer with k type thermocouple was used to measure

the temperature inside a temperature chamber. The temperature
controller of the chamber was set at 500 ° C
Dry Block
Calibrators
57
Digital Thermometer specification

Resolution: 0.1 °C
Type K accuracy ; ± 0.6 ° C
Thermocouples
Type: K
Last Calibration report uncertainty
± 2.0 ° C (99% CL).
The Correction at 500 ° C is 0.5 °C
58
When the temperature chamber indicator reached 500 °C, the readings
were taken after a stabilization time of half an hour. Ten measurements
were taken as recorded in table
Measurement Temperature in ° C Measurement Temperature in °C
1 500.1 6 500.0
2 500.0 7 500.1
3 501.1 8 500.2
4 499.9 9 499.9
5 499.9 10 500.0
Mathematical model : T = D+ Correction

T = temperature measured, D = Displayed of the thermometer
59
Mean deviation : t/ n = 500.2/10 = 500.02 x
Standard Deviation : s (t) = {1/(n-1)  (tj –t) 2}

= =  0.0106 ° C = 0.103 ° C 
Standard Error of the mean : S (t) =  s2 (t) / n =0.03 ° C
Standard Uncertainty u(t) =0.03 ° C u(t)
60
From specifications, the uncertainty in the thermometer is ± 0.6 ° C, u1
From calibration report, with a confidence level of 99% the uncertainty in u2

the thermocouple is ± 2.0 ° C (99% CL).
61
Sources of Estimates (Xi) Probability Standard Uncertainty

Uncertainty Distribution Contribution
°C Uncertainty
Type A or B °C
Digital 0.6 Type B U (X1) /3
Thermometer 0.35
Thermocouple 2.0 Type B U (X1) /2.58 0.78
Repeatability () 0.103 Type A U (XN)/10 0.03
Uc= 0.85
 (u12+u22+U32)
Expanded K=2 1.7
uncertainty
2 x 0.85 =
Temperature of the chamber was measured to be 500.5°C : The

measurement uncertainty is ±1.7 ° C
(With a coverage factor k =2 for confidence level of 95.4 %)
62
We discuss the method of calibration of 4 ½ digital multimeter for its

100 V range with the application of 10 v from calibrated direct volt
calibrator
63
We have the following inputs

1. The calibrator is calibrated regularly at the interval of six months for the range of
10 v, the specifications are resolution 10 v, with the uncertainty at 99 % CL as 4.5
 v of output + 100  v
2. 4½ digital mutlimeter specifications are : for range 100 V full display is 99.99 with
resolution = 10 mV and the uncertainty at 99 % level of confidence as ± (10-5 of
reading +0.2 X 10 –5 of full scale)
Vx= Voltage indicated in the DMM

The mathematical model: Vx= Vs+ Vx Vs= Voltage indicated from the calibrator
Observations:  Vx= Error of the multimeter
Applied voltage from Indicated voltage in DMM

Calibrator
10.00000V 10.01 V
64
Even after repetition of the readings of the mutlimeter

reading indicating the same value or ± 1 due to digitizing
process, this is due to better accuracy of the reference
standard (calibrator). In this case type A uncertainty can
be assumed as negligible
65
The uncertainty in applied voltage from the calibrator is

a1 = 4.5  v of output + 100  v = (4.5 x 10+100)  v = 145  v
From multimeter specification in the 100 V range, resolution is 10 mV

(i.e 1 count) Since the reading was unchanged and assuming the limit to be
half the count
a2= 10/2 mV = 5 mV
66
Sources of Estimates (Xi) Probability Standard Uncertainty Uncertainty

Uncertainty Distribution Contribution
Type A or B
v
Calibrator 145  V Type B U (X1) /2.58 56.20

uncertainty
Uncertainty of 5 mV Type B U (X1) /2.58 2886.75

the mutlimeter
Repeatability () 00 Type A 00
Uc= 2.89 mV
 (u12+u22+U32)
Expanded K=2 5.78 mV

uncertainty
2 x 2.89 mV =
67

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MEASUREMENT OF UNCERTAINTY

2)Based on Calibration Uncertainty

Example : Accuracy of the balance 0.0002g

Accuracy is rectangular hence Ua =0.0002/√3 = 0.0001154g

Resolution is rectangular hence Ur= 0.0001/ √3 = 0.0000577g

Uncertainty from calibration certificate =0.0006 k factor =2

Then Uncertainty is √ (Ua)2 + (Ur)2 +(Uc )2

Then Uncertainty is √(0.0001154)2 + (0.0000577)2 + (0.0003)2 =

If mass is taken by difference then Uncertainty is multiplied by

Standard Total Weight = Uncertainty = Standard

C8 0.00046(0.0008/sq3) 12.011 x 8 = 0.00046

H5 0.00004(0.00007/ 1.00794 x 5 = 0.00004 x 5 = 0.0002

O4 0.00017(0.0003/sq3) 15.9994 x 4 = 0.00017 x 4 = 0.00068

K 0.000058(0.0001/ 39.083 x 1 = 0.000058 x 1 =

Molecular weight of KHP = 96.088 + 5.0397 + 63.9976 +39.0983 =

Uncertainty with formula weight =Sqrt (0.003682+ 0.0002 2+ 0.000682 +

Note : Temperature Variation is ±3 co-efficient of expansion of water is 2.1 x 10 -4 / deg

For Burette at Different Volume Uncertainty is calculated by

Uncertainty Value Distribution Uncertainty

Note : Temperature Variation is ±3 co-efficient of expansion of water is 2.1 x 10 -4 /

c. Volumetric Flask, 100 ml

Uncertainty Value Distribution Uncertainty

Repeatability σ√6 0.002

Temperature 100x 3 x 2.1 x 10-4 = Rectangular 0.064/sqrt3 =0.037

Combined Uncertainty = Sqrt (0.0412+ + 0.0022 + 0.0372) = 0.055ml

Note : Temperature Variation is ±3 co-efficient of expansion of water is 2.1 x 10 -4 / deg

Purity Uncertainty Distribution Standard

a) 99.9 ± 0.1 Rectangular 0.1/sq3=0.058

b) 99.9min 100 max ± 0.1 Triangular 0.1/sq6=0.041

c) 99.9 ± 0.1,95% ± 0.1 Normal 0.1/2 = 0.05

(A) ESTIMATION OF UNCERTAINTY IN

(B) UNCERTAINTY EVALUATION USING PRIOR

Volume of water taken,ml A 25 25 25 25 25 25

Normality of Hcl,N 0.04968 0.04968 0.04968 0.04968 0.04968 0.04968

Average value ,mg/l 307.45

Standard deviation σ 5.43

1)Due to Sample Volume,ml (Pipette)

2)Due to Volume of Hcl Consumed,ml (Burette Reading,ml)

3)Due to normality of Hcl

4)Due to molecular weight of CaCO3

Fish Bone Diagram

Fish Bone Diagram

Calculation of Uncertainty in normality of Hcl

d)Uncertainty due to purity of standard (Sodium Carbonate)

Effective Degrees of Freedom

Therefore Uncertainty in Alkalinity Estimation is

Ash content in Chilly powder

σ about mean= σ/√6 0.00763 Type A Uncertainty UA

1)Due to Sample weight

2)Due to Residue weight

3)Due to Temperature Tolerance of ±20 degree centigrade

4)Due to Muffle Furnace Temperature Tolerance

Calculation of Uncertainty Type B

Muffle Furnace Temperature

Effective Degrees of Freedom

(UA) 4/5 + (UM) 4/∞+ (UR) 4/∞+ (UT) 4/∞+ (UF) 4/ ∞

Effective Degrees of Freedom 10479 ≈ ∞

Uncertainty in Benzoic Acid Estimation By HPLC

Volume made up , ml A 100 100 100 100 100 100

and Uncertainty is 2Sr = 20.74 =1.48%