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Ch6 0915 2023

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26 views52 pages

Ch6 0915 2023

Uploaded by

氣飛
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Fundamentals of

Analytical
Chemistry Eighth Edition
CHAPTER

Random Errors in
Chemical Analysis
Normal distribution
(a) The mean occurs at the central point of max frequency
(b) A symmetrical distribution of positive and negative deviations
about the max.
(c) Exponential decrease in frequency as the magnitude of the
deviation decrease
Figure 6-1
Three-dimensional plot showing absolute error in Kjeldahl nitrogen
determination for four different analysts.
Note that the results of analyst 1 are both precise and accurate.
The results of analysts 2 are imprecise but accurate.
The results of analyst 3 are precise, but the absolute error is large.
The results of analysts 4 are both imprecise and inaccurate.
relatively high precision and high accuracy

poor precision but good accuracy

excellent precision, but error occurs

both precision and accuracy are poor


Imaging a situation in which just 4 small random errors combine
to give an overall error, assuming each error has an equal probability
of occurring to cause the final result to be high or low by fixed
amount ± U
0 U 0.375
2 U 0.25
4 U 0.065

Figure 6-2
Frequency distribution for
measurements containing
(a) 4 random uncertainties;
(b) 10 random
uncertainties; (c) a very
large number of random
uncertainties.

Such as plot is called a Gaussian


curve, or normal error curve
Figure 6-3
A histogram (A) showing distribution of
the 50 results in Table 6-3 and a
Gaussian curve (B) for data having the
same mean and standard deviations as
the data in the histogram.
Histogram

A Gaussian, or normal error curve is a curve that shows the


symmetrical distribution of data around the mean of an infinite set
of data
Sources of random uncertainties in the calibration
of a pipet
https://www.youtube.com/watch?app=desktop&v=zIHXxCIL6ps
(1) Visual judgment
(2) Variation in the drainage time and in the angle of
the pipet as it drains
(3) Temperature fluctuation
(a) Affect the volume of the pipet
(b) The viscosity of the liquid
(c) Performance of the balance
(4) Vibrations and drafts that cause small variations in
the balance readings
Figure 6F-1 Results of a coin-flipping experiment
(flip a coin 10 times) by 395 student over an 18-
year period.

Number of Heads 0 1 2 3 4 5 6 7 8 9 10
Frequency 1 1 22 42 102 104 92 48 22 7 1
Figure 6-4
Normal error curves. The standard deviation for curve
B is twice that for curve A; that is, σB=2σA. (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 σ. Thus, the two curves A
and B are identical here.
the deviation from the mean
in units of σ.
The precision of the
data set leading to
curve A is twice as
good as that of the
data set represented
by curve B
The breadth of these curves is a measure of the
precision of the different sets of data
Z, a new variable, is
the deviation of a
data point from the
mean relative to one
standard deviation.

is the deviation from the


mean in units of σ
Areas under a Gaussian Curve
Population mean () vs. sample mean X
The sample mean is the arithmetic average of a
limited sample drawn from a population of data,
which is defined as the sum of the measurements
divided by the number of measurements.

drawn

The population mean is the true mean for the


population.
Population standard deviation, σ
Calculation of sample standard
deviation
The number of degrees of freedom
is a measure of the number of
independent pieces of information on
which the precision of a parameter
estimate is based
Spreadsheet Exercise (homework)
D11/(N-1)

0.354495
B13/B12 x 1000

Chapter 6 p122
Standard error of the mean
每次的抽樣結果與母群體間的偏差

The standard error of a mean, Sm, is the standard deviation of a set


of data divided by the square root of the number of data points in
the set.
Pooling data to improve the
reliability of s (σ)

Better estimate of the population


standard deviation by pooling
(combining) the data than by using only
one data set
The pooled estimate of σ, also called spooled,
is a weighted average of the individual
estimates.

To calculate spooled, deviations from the mean for


each subset are squared, the squares of the
deviations of all subsets are then summed and
divided by the appropriate number of degrees
of freedom
Pooled estimate of the std dev
The number of degrees of freedom
is a measure of the number of
independent pieces of information on
which the precision of a parameter
estimate is based
A glucose analyzer
Example 6-2
Time Glucose Mean Sum of Standard
Conc, mg/L Glucose, squares of deviation
mg/L Deviation
from Mean
Month 1 1108, 1122, 1075, 1100.3 1687.43 16.8
1099, 1115, 1083,
1100 (7)
Month 2 992, 975, 1022, 996.2 1182.80 17.2
1001, 991 (5)
Month 3 788, 805, 779, 798.8 1086.80 16.5
822, 800 (5)

Month 4 799, 745, 750, 771.9 2950.86 22.2


774, 777, 800,
758 (7)
Total N 7+5+5+7=24 6907.89
Total number of measurements = 24
Total sum of squares = 6907.89
Degree of Freedom = 24-4 = 20
spooled = √ (6907.89/(24-4)
Variance and other measures
of precision
• Variance (s2) – the square of the standard
deviation
• The sample variance, s2,is an estimate of the
population variance, σ2
• Relative standard deviation (RSD)(sr) and
coefficient of variation (CV)
• Spread or Range (w) – the difference between
the largest value and the smallest in the data set
Never round a standard deviation calculation
until the very end.

As N  , x  , and s  
s is nearly equal to  for N >20
Significant Figures
The significant figures in a number are all of
the digits known with certainty plus the first
uncertain digit.

30.2~30.3 mL

Figure 6-5
Buret section showing the liquid
level and meniscus.
Significance figures
• Disregard all initial zeros
• Disregard all final zeros unless they follow a decimal
point
• All remaining digits, including zeros between non-zero
digits, are significant
• Sums and difference (3.4+0.020+7.31=10.730  10.7)
– The result should contain the same number of decimal
places as the number with the smallest number of decimal
places
• Products and quotients (24x4.02/100.0 = 0.965 0.96)
– The result should contain the same number of significant
digits as the original number with the smallest number of
significant digits  sometimes leads to incorrect rounding
– Assuming a unit uncertainty in the last digit of each number
– 6D-2 significant figures in numerical computation
Rounding Data
• Page 117
• 0.635  0.64; 0.625  0.62
• Rounding a 5 is always to round to the
nearest even number
• Postpone rounding until the calculation is
completed

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