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Chapter 5-7
Errors, Random Errors, and Statistical
Data in Chemical Analyses

¡  Impossible: The analytical results are free of errors or

uncertainties.
¡  Possible: Minimize these errors and estimate their size with
acceptable accuracy.
¡  Statistical calculations for use to judge the quality of
experimental measurements are many.

Error （偏差，誤差）:
1)  The difference between a measured value and the “true” or
“known” value.
2)  The estimated uncertainty in a measurement or experiment.

3-2

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Figure 5-1 Results from six replicate determinations for iron in aqueous
samples of a standard solution containing 20.00 ppm of iron(III).

3-3

¡  Measurements are always accompanied by uncertainty. The

true value always falls within a range due to uncertainty. The
true value for any quantity is always unknown.

¡  The probable magnitude of the error can be evaluated. We

can then defines the limit within which the true value of a
measured quantity lies at a given level of probability.
¡  Data of unknown quality are worthless. (reliability of data)
¡  The true value of a measurement is never known exactly.

3-4

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¡  Standards of known composition can be analyzed and the

results compared with the known composition.
¡  Consult the literature.
¡  Calibrating equipment enhances the quality of data.
¡  Finally, statistical tests can be applied to the data.

3-5

¡  Questions to answer before beginning an analysis:

§  What is the maximum error that I can tolerate in the result?
No one can afford to waste time generating data that are
more reliable than is needed.

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¡  Mean (均值), arithmetic mean, and average (x) are synonyms.

(5-1)

where xi represents the individual values of x making up a set

of N replicate measurements.

The symbol Σxi means to add all the values xi for the
replicates.

3-7

¡  The median (中值) is the middle result when replicate data

are arranged in order of size.
¡  Equal numbers of results are larger and smaller than the
median.
¡  For an odd number of data points, the median can be
evaluated directly. For an even number, the mean of the
middle pair is used.

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¡  The mean of two or more measurements is their average

value.
¡  The median is used advantageously when a set of data
contains an outlier (離群值, 異常值), a result that differs
significantly from others in the set.

3-9

¡  Calculate the mean and the median for the data shown in Figure 5-1.

Because the set contains an even number of measurements, the

median is the average of the central pair:

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Figure 5-1 Results from six replicate determinations for iron in aqueous
samples of a standard solution containing 20.00 ppm of iron(III).

3-11

¡  Precision (精確度，精密度) describes the reproducibility of

measurements; the closeness of results to each other.
¡  Precision is determined by repeating the measurement on
replicate samples.
¡  Three terms to describe the precision of a set of replicate data:
standard deviation (σ), variance (σ2), and coefficient of variation
(CV).

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¡  Precision is a function of the deviation from the mean di, or

just the deviation, which is defined as

(5-2)

¡  Precision is the closeness of results to others that have

been obtained in exactly the same way.

3-13

¡  Accuracy (準確度) indicates the closeness of the

measurement to its true or accepted value and is expressed
by the error.
§  Accuracy measures agreement between a result and its
true value.
§  Precision describes the agreement among several results
that have been obtained in the same way.

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Figure 5-2 Illustration of accuracy and precision using the

pattern of darts on a dartboard
3-15

¡  Absolute Error
§  The absolute error E in the measurement of a quantity xi is
given by the equation
(5-3)

where xt is the true, or accepted, value of the quantity.

Note that we retain the sign in stating the error.
¡  Relative error
§  Often, the relative error Er is a more useful quantity than
the absolute error. The percent relative error is given by the
expression
(5-4)

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¡  Relative error
§  Relative error is also expressed in parts per thousand (ppt).

e.g.

3-17

¡  To determine accuracy, we have to know the true value, and

this value is exactly what we are seeking in the analysis.
¡  Results can be precise without being accurate and accurate
without being precise.
¡  The danger of assuming that precise results are also
accurate is illustrated in Figure 5-3, which summarizes the
results for the determination of nitrogen in two pure
compounds: benzyl isothiourea hydrochloride (苄異硫脲鹽酸
鹽) and nicotinic acid (菸鹼酸).

3-18

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NH
S O
NH3Cl
OH

N
benzyl isothiourea hydrochloride nicotinic acid

Figure 5-3 Absolute error in the micro-Kjeldahl determination of nitrogen (凱氏定氮法).

Each dot represents the error associated with a single determination. Each vertical line
labeled (xi - xt ) is the absolute average deviation of the set from the true value. (Data from
C. O. Willits and C. L. Ogg, J. Assoc. Anal. Chem., 1949, 32, 561. With permission.)
3-19

absolute average
deviation = 0.22

Figure 5-1 Results from six replicate determinations for iron in aqueous
samples of a standard solution containing 20.00 ppm of iron(III).

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¡  Figures 5-1 and 5-3 suggest that chemical analyses are

affected by at least two types of errors.

¡  One type, called random (or indeterminate不確定) error

(隨機誤差), causes data to be scattered more or less
symmetrically around a mean value.

¡  Refer to Figure 5-3: Notice that the scatter in the data, and
thus the random error, for analysts 1 and 3 is significantly
less than that for analysts 2 and 4.

3-21

¡  A second type of error, called systematic (or

determinate) error (系統誤差), causes the mean of a
set of data to differ from the true or accepted value.

¡  The results of analysts 1 and 2 in Figure 5-3 have little

systematic error, but the data of analysts 3 and 4 show
systematic errors of about 0.7 and 1.2% nitrogen.

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¡  Random (indeterminate) errors are errors that affect the

precision (精確度) of measurement.

¡  Systematic (determinate) errors affect the accuracy (準

確度) of results.

3-23

¡  A third type of error is gross error (過失誤差). Gross errors

differ from indeterminate and determinate errors. They
usually occur only occasionally, are often large, and may
cause a result to be either high or low.
¡  Gross errors lead to outliers (離群值, 異常值), results that
appear to differ markedly from all other data in a set of
replicate measurements. (often the product of human errors)
¡  Various statistical tests can be done to determine if a data
point is an outlier.

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¡  Systematic errors have a definite value, an assignable

cause, and are of about the same magnitude for
replicate measurements made in the same way.

¡  Systematic errors lead to bias (偏誤，偏差) in

measurement results. Note that bias affects all the data
in a set in approximately the same way and that it bears
a sign.

3-25

¡  Three types of systematic errors:

§  (1) Instrument errors are caused by imperfections in
measuring devices and instabilities in their components.
§  (2) Method errors arise from non-ideal chemical or
physical behavior of analytical systems.
§  (3) Personal errors result from the carelessness,
inattention, or personal limitations of the experimenter.

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¡  Instrument errors
§  All measuring devices are sources of systematic errors.
For example, pipets, burets, and volumetric flasks may
hold or deliver volumes slightly different from those
indicated by their graduations.
§  These differences arise from using glassware at a
temperature that differs significantly from the calibration
temperature, from distortions in container walls due to
heating while drying, from errors in the original calibration,
or from contaminants or scratches on the inner surfaces of
the containers. Calibration eliminates most systematic
errors of this type.

3-27

¡  Instrument Errors
§  Electronic instruments are subject to instrumental
systematic errors. These uncertainties have many
sources. For example, errors emerge as the voltage of a
battery-operated power supply decreases with use.
Instrument errors are detectable and correctable.

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¡  Method Errors
§  The non-ideal chemical or physical behavior of the
reagents and reactions upon which an analysis is
based often introduce systematic method errors.

§  Such sources of non-ideality include the slowness

and incompleteness of reactions, the instability of
species, non-specificity of most reagents, and
possible interference.

3-29

¡  Method Errors
§  In Figure 5-3, the results by analysts 3 and 4 show a
negative bias that can be traced to the chemical nature of
the sample, nicotinic acid.
§  The compounds containing a pyridine ring are incompletely
decomposed by the sulfuric acid; hence, the negative
errors in Figure 5-3 are likely systematic errors from
incomplete decomposition of the samples.
§  Errors inherent in a method are often difficult to detect and
are thus the most serious of the three types of systematic
error.

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NH
S O
NH3Cl
OH

N
benzyl isothiourea hydrochloride nicotinic acid

Figure 3-3 Absolute error in the micro-Kjeldahl determination of nitrogen (凱氏定氮法).

Each dot represents the error associated with a single determination. Each vertical line
labeled (xi - xt ) is the absolute average deviation of the set from the true value. (Data from
C. O. Willits and C. L. Ogg, J. Assoc. Anal. Chem., 1949, 32, 561. With permission.)
3-31

Kjeldahl method
The Kjeldahl method or Kjeldahl digestion is a method for the
quantitative determination of nitrogen in chemical substances.

Degradation:
Sample + H2SO4 → (NH4)2SO4(aq) + CO2(g) + SO2(g) + H2O(g)
Liberation of ammonia:
(NH4)2SO4(aq) + 2NaOH → Na2SO4(aq) + 2H2O(l) + 2NH3(g)

Capture of ammonia:
B(OH)3 + H2O + NH3 → NH4+ + B(OH)4–
Back-titration:
B(OH)3 + H2O + Na2CO3 → NaHCO3(aq) + NaB(OH)4(aq) + CO2(g) + H2O
NH
S O
NH3Cl
OH

N
benzyl isothiourea hydrochloride nicotinic acid
1-32

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¡  Personal Errors
Measurements requiring personal judgments.
§  Judgments of this type are often subject to systematic,
unidirectional errors.
§  An analyst who is insensitive to color changes tends to use
excess reagent in a volumetric analysis. Physical
disabilities are often sources of personal determinate
errors.
§  A universal source of personal error is prejudice or bias.

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¡  Personal Errors
Number bias is another source of personal error that varies
considerably from person to person.

§ The most common number bias encountered in estimating

the position of a needle on a scale involves a preference for
the digits 0 and 5. Also prevalent is a prejudice favoring small
digits over large and even numbers over odd.

§ Color blindness amplifies personal errors in a volumetric

analysis.

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Systematic errors may be either constant or proportional.

¡  The magnitude of a constant error does not depend on the

size of the quantity measured. Absolute error is constant, but
relative error varies with sample size. (ex. solubility loss)

¡  Proportional errors increase or decrease in proportion to the

size of the sample taken for analysis. Absolute error varies with
sample size, but relative error stays constant. (interfering
contaminants) (p. 89)

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¡  Systematic instrument errors are usually corrected by

periodic calibration of equipment. The response of most
instruments changes with time.

¡  Most personal errors can be minimized by care and self-

discipline.

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¡  Bias (偏誤，偏差) in an analytical method is particularly

difficult to detect. One or more of the following steps can
recognize and adjust for a systematic error in an analytical
method.

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¡  Analysis of Standard Samples

§  Analyzing standard reference materials, SRM, is the best
way to estimate the bias of an analytical method.

§  The SRM Materials contain one or more analytes at well-

known or certified concentration levels.

§  Standard materials can sometimes be prepared by

synthesis.

§  Standard reference material can be purchased from a

number of governmental and industrial sources.

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§  The concentration of one or more of the components in

these materials has been determined in one of three ways:
▪  (1) by analysis with a previously validated reference
method;
▪  (2) by analysis by two or more independent, reliable
measurement methods;
▪  (3) by analysis by a network of cooperating laboratories
that are technically competent and thoroughly
knowledgeable with the material being tested.

3-39

Standard reference materials

from NIST. (Photo courtesy of
the National Institute of
Standards and Technology.)

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¡  Independent Analysis
§  If standard samples are not available, a second
independent and reliable analytical method can be used in
parallel with the method being evaluated.

§  A statistical test must be used to determine whether any

difference is a result of random errors in the two methods
or due to bias in the method under study.

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¡  Performing Blank Determinations

§  Blank determinations are useful for detecting certain types
of constant errors.
§  In a blank determination, or blank, all steps of the analysis
are performed in the absence of a sample.
§  The results from the blank are then applied as a correction
to the sample measurements.
§  Blank determinations reveal errors and correct data.

n  Variation in Sample Size

Constant errors can often be detected by varying the sample size.

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¡  Describe three types of errors in experimental data.

¡  Explain the sources of systematic errors.

¡  Explain absolute error and relative error.

¡  Define bias.

1-43

¡  All measurements contain random errors.

§  Random, or indeterminate, errors occur whenever a
measurement is made.
§  Caused by many small but uncontrollable variables.

§  The errors are accumulative.

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Analysts 2 & 4: larger random error.

¡  Figure 6-1 A three-dimensional plot showing absolute error in

Kjeldahl nitrogen determinations for four different analysts.

1-45

¡  Imagine a situation in which just four small random

errors combine to give an overall error.

¡  We will assume that each error has an equal probability

of occurring and that each can cause the final result to
be high or low by a fixed amount ±U.

¡  Table 6-1 shows all the possible ways the four errors
can combine to give the indicated deviations from the
mean value.

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3-47

Figure 6-2 Frequency distribution for

measurements containing (a) four random
uncertainties, (b) ten random uncertainties,
and (c) a very large number of random
uncertainties.

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(c)

¡  For a very large number of individual errors, a bell-shaped

curve like that shown in Figure 6-2c results. Such a plot is
called a Gaussian curve (高斯曲線) or a normal error curve
(正態誤差曲線).
3-49

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¡  This 0.025 mL spread of data, from a low of 9.969 mL to

a high of 9.994 mL, results directly from an accumulation
of all the random uncertainties in the experiment.

¡  Rearrange Table 6-2 into frequency distribution groups,

as in Table 6-3.

3-51

26% of the data reside in the cell containing the mean and median
value of 9.982 mL and that more than half the results are within ±
0.004 mL of this mean.

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¡  The frequency distribution data in Table 6-3 are plotted

as a bar graph (條形圖), or histogram (直方圖)(labeled
A in Figure 6-5). As the number of measurements
increases, the histogram approaches the shape of the
continuous curve shown as plot B in Figure 6-3 (a
Gaussian curve, or normal error curve).

3-53

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 deviation as the data in the histogram.

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¡  Many small and uncontrollable variables affect even the

simple process of calibrating a pipet.
¡  The cumulative effect of random uncertainties is
responsible for the scatter of data points around the
mean.
¡  Statistics only reveal information that is already present
in a data set.

3-55

¡  (1) visual judgments, such as the level of the water with

respect to the marking on the pipet and the mercury level in
the thermometer

¡  (2) variations in the drainage time and in the angle of the

pipet as it drains

¡  (3) temperature fluctuations, which affect the volume of the

pipet, the viscosity of the liquid, and the performance of the
balance

¡  (4) vibrations and drafts that cause small variations in the

balance readings.

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¡  The random, or indeterminate, errors in the results of an

analysis can be evaluated by the methods of statistics.

¡  Ordinarily, statistical analysis of analytical data is based on

the assumption that random errors follow a Gaussian, or
normal, distribution.

¡  Sometimes analytical data depart seriously from Gaussian

behavior, but the normal distribution is the most common.

¡  We base this discussion entirely on normally distributed

random errors.

3-57

¡  In statistics, a finite number of experimental

observations is called a sample of data (數據樣本); this
is different from the term used in chemical analysis.

¡  A population (母體) (or a universe): the collection of all

measurements of interest to the experimenter [finite
and real, or conceptual and infinite]. A sample is a
subset of measurements selected from the population.

¡  Statistical laws must be modified when applied to a

small sample because a few data points may not be
representative of the population.

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¡  Figure 6-4a shows two Gaussian curves in which the relative

frequency y of occurrence of various deviations from the mean
is plotted as a function of the deviation from the mean.
¡  The equation for a Gaussian curve has the form

¡  The equation contains just two parameters, the population

mean µ and the population standard deviation σ.

3-59

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.

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(b) The abscissa is the deviation from the mean in units of

σ. Thus, the two curves A and B are identical here.

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•  The Population Mean µ and the Sample Mean x

Sample mean = x, where

when N is small

– Population mean = µ, where

when N → ∞

The difference between x and µ decreases rapidly as N

reaches over 20 to 30. In the absence of systematic error,
the population mean (µ) is also the true value (xt) for the
measured quantity.
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¡  The Population Standard Deviation (σ)

§  σ is a measure of the precision or scatter of a population
of data, which is given by the equation

(6-1)

where N is the number of data points making up the

population.

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¡  The Population Standard Deviation (σ)

§  The two curves in Figure 6-4a are for two populations of
data that differ only in their standard deviations (σ).
§  The standard deviation for the data set yielding the broader
but lower curve B is twice that for the measurements
yielding curve A (σB = 2σA).
§  The precision of the data leading to curve A is twice as
good as that of the data that are represented by curve B.

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¡  The Population Standard Deviation (σ)

§  Figure 6-4b shows another type of normal error curve in
which the abscissa is now a new variable z, which is
defined as
(6-2)

z is the deviation of a data point from the mean relative to

one standard deviation. That is, when x – µ = σ, z is equal
to one; when x – µ = 2σ, z is equal to two.
2/2 σ 2 2
e−( x−µ ) e−z /2
y= =
σ 2π σ 2π
3-65

¡  The Population Standard Deviation (σ)

§  A plot of relative frequency versus this parameter (z) yields
a single Gaussian curve that describes all populations of
data regardless of standard deviation.

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¡  The Population Standard Deviation (σ)

§  Variance (變異數): The square of the standard deviation σ2.
§  A normal error curve (正態誤差曲線) has several general
properties:
▪  (1) The mean occurs at the central point of maximum
frequency,
▪  (2) there is a symmetrical distribution of positive and
negative deviations about the maximum,
▪  (3) there is an exponential decrease in frequency as the
magnitude of the deviations increases.
§  Small random uncertainties are more common.

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¡  Equation 6-1 must be modified for a small sample of data.

Thus, the sample standard deviation s is given by the equation
¡ 

(6-4)

¡  The quantity N - 1 is called the number of degrees of freedom

(the number of independent results that enter into the
computation of the s).

¡  Population standard deviation:

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•  An Alternative Expression for Sample Standard

Deviation

(6-5)

(6-4)

3-69

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. Calculate the mean and the standard
deviation of this set of data.
2 2
To apply Equation 6-5, we calculate ∑x i
and (∑ x i ) / N

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Substituting into Equation 6-5 leads to

3-71

¡  Note in Example 6-1 that the difference between Σx2i and

(Σxi)2/N is very small. If we had rounded these numbers
before subtracting them, a serious error would have appeared
in the computed value of s. To avoid this source of error,
never round a standard deviation calculation until the very
end.

(6-5)

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Gaussian Curve

Area: probability of a measured value

occurring between those limits. (the
chance that the random uncertainty of
any single measurement is no more
than ±nσ.

1-73

¡  Standard Error of the Mean

§  For replicate samples, each containing N measurements, are taken
randomly from a population of data, the mean of each set will show
less and less scatter as N increases.
§  The standard deviation of each mean is known as the standard error
of the mean (SEM，平均值標準誤差) and is given the symbol sm.

(6-6) sm α s and sm α 1/N1/2

The precision can be enhanced by decreasing S or increasing N

(p. 105).

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¡  The Population Standard Deviation (σ)

§  A plot of relative frequency versus this parameter (z) yields
a single Gaussian curve that describes all populations of
data regardless of standard deviation.

3-75

¡  The rapid improvement in the reliability of s with increases in N

makes it feasible to obtain a good approximation of σ when the
method of measurement is not excessively time consuming and
when an adequate supply of sample is available.

¡  When N is greater than about 20, s and σ can be assumed to be

identical.

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•  Pooled data (合併數據，綜合數據) from a series of

similar samples accumulated over time provide an estimate of s
that is superior to the value for any individual subset.

•  Assume the same sources of random error in all the

measurements.

•  To obtain a pooled estimate of the standard deviation, spooled,

deviations from the mean for each subset are squared; the squares
of all subsets are then summed and divided by an appropriate
number of degrees of freedom.

3-77

¡  The equation for computing a pooled standard deviation from

several sets of data takes the form

where N1 is the number of results in set 1, N2 is the number in set 2,

and so forth. The term Nt is the number of data sets that are pooled.

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3-79

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¡  Other than sample standard deviation, three other terms are often
employ in reporting the precision.
1.  The variance (s2) is

(6-8)

¡  People who do scientific work tend to use standard deviation rather

than variance as a measure of precision.

3-81

2.  Relative standard deviation:

s s
RSD = s r = RSDinppt = × 1000 ppt
x x

3.  Coefficient of variation (CV)

s
CV = RSDinperce nt = × 100% (6-9)
x

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¡  Spread or Range (w)

§  Another term to describe the precision of a set of replicate results.
§  It is the difference between the largest value in the set and the
smallest.
§  Example: The spread of the data is (20.3 -19.4) = 0.9 ppm Fe.

Figure 3-1 Results from six replicate

determinations for iron in aqueous
samples of a standard solution containing
20.00 ppm of iron(III).

3-83

•  For the set of data in Example 6-3, calculate (a) the variance,
(b) the relative standard deviation in parts per thousand, (c)
the coefficient of variation, and (d) the spread.

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3-85

¡  Consider the summation

¡  The standard deviation of sum could be
as large as +0.02 + 0.03 + 0.05 = +0.10,
or as small as -0.02 - 0.03 - 0.05 = -0.10,
Absolute standard deviations
or any value lies between these two extremes,
or even -0.02 - 0.03 + 0.05 = 0, +0.02 + 0.03 - 0.05 = 0
•  The variance of a sum or difference is equal to the sum of
the individual variances.
•  If y = a + b – c, for the computation
The variance of y, sy2 is given by

sy = ±0.06 à 2.63±0.06

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3-87

As shown in Table 6-4, the relative standard deviation of a

product or quotient is determined by the relative standard
deviations of the numbers forming the computed result.

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Applying this equation to the numerical example gives

we can write the answer and its uncertainty as 0.0104(±0.0003).

3-89

¡  One of the best ways of indicating reliability (信度) is to give a

confidence interval at the 90% or 95% confidence level.
¡  Another method is to report the absolute standard deviation or the
coefficient of variation (CV) of the data.
¡  A less satisfactory but more common indicator of the quality of data is
the significant figure (有效數字) convention.

¡  信度(reliability)是指測量結果的一致性、穩定性及可靠性。

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¡  A simple way of indicating the probable uncertainty associated with an

experimental measurement is to round the result so that it contains
only significant figures (有效數字).
¡  The significant figures in a number are all the certain digits plus the
first uncertain digit.
¡  A zero may or may not be significant depending on its location in a
number.
¡  A zero that is surrounded by other digits is always significant (such as
in 30.24 mL).
¡  Zeros that only locate the decimal point for us are not.

3-91

¡  Sums and Differences

For addition and subtraction, the number of significant figures can be
found by visual inspection.

the second and third decimal places in the answer cannot be

significant because 3.4 is uncertain in the first decimal place.

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¡  Products and Quotients

A rule of thumb sometimes suggested for multiplication and division
is that the answer should be rounded so that it contains the same
number of significant digits as the original number with the smallest
number of significant digits.

Ex.

3-93

The first answer would be rounded to 1.1 and the second to

0.96. If we assume a unit uncertainty in the last digit of each
number in the first quotient, however, the relative uncertainties
associated with each of these numbers are 1/24, 1/452, and
1/1000.

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Because the first relative uncertainty is much larger than the

other two, the relative uncertainty in the result is also the
absolute uncertainty is then

Therefore, the first result should be rounded to three significant

figures or 1.08, but the second should be rounded to only two;
that is 0.96.

3-95

¡  Logarithms and Antilogarithms

1.  In a logarithm of a number, keep as many digits to the right
of the decimal point as there are significant figures in the
original number.
2.  In an antilogarithm of a number, keep as many digits as
there are digits to the right of the decimal point in the
original number.

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Round the following answers so that only significant digits are

retained: (a) log 4.000 Í 105 = 4.3979400 and (b) antilog 12.5
= 3.162277 Í 1012.
(a)  Following rule 1, we retain 4 digits to the right of the
decimal point

(b) Following rule 2, we may retain only 1 digit

3-97

¡  A good guide to follow when rounding a 5 is always to round

to the nearest even number. For example, 0.635 rounds to
0.64 and 0.625 rounds to 0.62.
¡  We should note that it is seldom justifiable to keep more than
one significant figure in the standard deviation because the
standard deviation contains error as well.

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¡  The uncertainty of the result is estimated using the

techniques presented in Section 3E. Finally, the result is
rounded so that it contains only significant digits.

¡  It is especially important to postpone rounding until the

calculation is completed. At least one extra digit beyond the
significant digits should be carried through all the
computations to avoid a rounding error.

¡  This extra digit is sometimes called a “guard” digit.

3-99

¡  A statistical technique called regression analysis provides

the means for objectively obtaining such a line and also for
specifying the uncertainties associated with its subsequent
use.

迴歸分析(Regression Analysis)是一種統計學上分析數據的方
法，目的在於了解兩個或多個變數間是否相關、相關方向與
強度，並建立數學模型以便觀察特定變數來預測研究者感興
趣的變數。

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the vertical deviation of each point from the

straight line is called a residual (殘差).

Figure 8-9 Calibration curve of absorbance versus

analyte concentration for a series of standards.

1-101

¡  the method of least squares is used to generate a calibration curve

(working curve), two assumptions are required. The first is that
there is actually a linear relationship between the measured variable
(y) and the analyte concentration (x).
¡  The mathematical relationship that describes this assumption is
called the regression model, which may be represented as

¡  where b is the y intercept (the value of y when x is zero) and m is the

slope of the line.

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The second assumption: any deviation of the individual points from the
straight line arises from error in the measurement. That is: no error in x
values of the points (concentration).

¡  The least-squares method finds the sum of the squares of the

residuals SSresid and minimizes the sum using calculus.

N 2

SS resid = ∑ [yi − (b + mxi )]

i =1

1-103

(8-10)

(8-11)

(8-12)

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¡  1. The slope of the line m: (8-13)

(8-14)
¡  2. The intercept b:

¡  3. The standard deviation about regression sr:

(3-24)
(8-15)

3-105

¡  4. The standard deviation of the slope sm :

(8-16)

¡  5. The standard deviation of the intercept sb :

(8-17)

¡  6. The standard deviation for results obtained from the

calibration curve sc:
yc: mean of a set of M (8-18)
replicate analysis.
y: mean for the N
calibration points
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¡  The standard deviation about regression sr (Equation 8-15) is

the standard deviation for y when the deviations are
measured not from the mean of y (as is usually the case) but
from the straight line that results from the least-squares
analysis:

¡  The standard deviation about regression is often called the

standard error of the estimate or the standard error in y.

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55