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a b c
Fig. 6-2 Frequency distribution for measurements containing (a) 4 random
uncertainties; (b) 10 random uncertainties and (c) a very large number of random
uncertainties.
6A-2 Distribution of experimental data
Table 6-2 Replicate Data on the Calibration of a 10-mL Pipet
Trial mL Trial mL Trial mL Trial mL Trial mL Trial mL
1 9.988 10 9.990 19 9.980 28 9.991 37 9.988 46 9.978
2 9.973 11 9.980 20 9.994 29 9.981 38 9.971 47 9.983
3 9.986 12 9.989 21 9.992 30 9.969 39 9.986 48 9.980
4 9.980 13 9.978 22 9.984 31 9.985 40 9.978 49 9.983
5 9.975 14 9.971 23 9.981 32 9.977 41 9.986 50 9.979
6 9.982 15 9.982 24 9.987 33 9.976 42 9.982
7 9.986 16 9.983 25 9.978 34 9.983 43 9.977
8 9.982 17 9.988 26 9.983 35 9.976 44 9.977
9 9.981 18 9.975 27 9.982 36 9.990 45 9.986
Mean volume = 9.982 mL Median volume = 9.982 mL
Spread = 0.025 mL Standard deviation = 0.0056 mL
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6B Statistical Treatment of Random Error
6B-1 Samples and Populations
6B-2 Properties of Gaussian Curves
a
b
Fig. 6-4 Normal error curves. The standard deviation for curve B is twice that for
curve A; that is, B = 2A. (a) The abscissa is the deviation from the mean in the units
of measurement. (b) The abscissa is the deviation from the mean in units of . Thus,
the two curves A and B are identical here.
N N N
( xi ) 2
( xi x) 2 (d i ) 2 x 2
i i =1
N
s= i =1
= i =1
= i =1
N 1 N 1 N 1
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s
Standard Error of the Mean: sm =
N
N N
2
Variance (s )
( xi x) 2 (di ) 2
s 2 = i =1 = i =1
N 1 N 1
Ex. 6-1 The following results were obtained in the replicate determination of the lead
content of a blood sample: 0.752, 0.756, 0.752, 0.751 and 0.760 ppm Pb.
1. Calculate the mean and the standard deviation of this set of data.
Sample xi xi2
x=
xi = 3.771 = 0.7542
1 0.752 0.565504 N 5
2 0.756 0.571536 0.754 ppb Pb
3 0.752 0.565504
4 0.751 0.564001 ( xi ) 2 (3.771) 2 14.220441
= =
5 0.760 0.577600 N 5 5
xi = 3.771 xi = 2.844145
2
= 2.8440882
2. Calculate the (a) variance, (b) relative standard deviation in parts per thousand,
(c) coefficient of variation and (d) spread.
(a) s2 = (0.0038)2 = 1.4 10-5
(b) RSD = 0.0038/0.754 1000 ppt = 5.0 ppt
(c) CV = 0.0038/0.754 100 % = 0.50 %
(d) w = 0.760 0.751 = 0.009 ppm Pb
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Ex. 6-2 Glucose levels are routinely monitored in patients suffering from diabetes.
The glucose concentrations in a patient with mildly elevated glucose levels were
determined in different months by a spectrophotometric analytical method. The
patient was placed on a low-sugar diet to reduce the glucose levels. The following
results were obtained during a study to determine the effectiveness of the diet.
Calculate a pooled estimate of the standard deviation for the method.
6907.89
pooled standard deviation: s pooled = = 18.58 19 mg/L
24 4
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6C-1 Standard Deviation of a Sum or Differences
*y = a ( Sa) + b ( Sb) - c ( Sc) s y = sa2 + sb2 + sc2
+ 0.02 + 0.03 + 0.05 = + 0.10
+ 0.50 ( 0.02)
+ 0.02 + 0.03 - 0.05 = - 0.02 - 0.03 + 0.05 = 0
+ 4.10 ( 0.03)
- 1.97 ( 0.05) - 0.02 - 0.03 - 0.05 = - 0.10
2.63 s y = (0.02) 2 + (0.03) 2 + (0.05) 2 = 0.06
the sum should be reported as 2.63 ( 0.06)
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6C-3 Standard Deviations in Exponential Calculations
Sy S
y = ax = x a
y a
Ex. 6-5 The standard deviation in measuring the diameter d of a sphere is 0.02 cm.
What is the standard deviation in the calculated volume V of the sphere if d
= 2.15 cm?
3 3
4 4 d 4 2.15
V = r 3 = = = 5.20 cm
3
3 3 2 3 2
SV S 0.02
= 3 d = 3 = 0.0279 , SV = 5.20 0.0279 = 0.145, V= 5.2 ( 0.1) cm3
V d 2.15
Ex. 6-6 The solubility product Ksp for the silver salt AgX is 4.0 ( 0.4) 10-8. The
molar solubility of AgX in water is
Solubility = (Ksp)1/2 =(4.0 10-8) 1/2 = 2.0 10-4 M
What is the uncertainty in the calculated solubility of AgX in water?
y = solubility, a = Ksp, x =
S a 0.4 10 -8 Sy 1 0.4
= , = = 0.05, Sy = 2.0 10-4 0.05 = 0.1 10-4
a 4.0 10 -8 y 2 4.0
Solubility = 2.0 ( 0.1) 10-4 M
Ex. 6-8 (1) log 4.000 10-5 = - 4.3979, (2) antilog 12.5 = 3 1012
(3) log 9.57 104 = 4.981
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(2) analytical balance : uncertainty = 0.0001 g
0.0001/3.4842 1000 ppt = 0.029 ppt
(3) the A.U. in the molarity of the reagent soln = 0.0001
0.0001/0.2328 1000 ppt = 0.43 ppt
(4) the R.U. in the molar mass of HBz is several orders of magnitude smaller
than that of the three experimental data and is of no consequence.
(5) 100 % and 1000 mmol are exact numbers
The answer is rounded so that its relative uncertainty lies between 0.2 and 2
times the largest relative uncertainty of the input data.
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