Analytical Chemistry

Chapter 2
Statistics in Analytical Chemistry- Part 1

Instructor: Nguyen Thao Trang

Outlines
• Errors in chemical analysis
– Important terms
– Significance figures
– Systematic errors
– Random errors

• Statistical treatment of random errors

– Gaussian distribution
– Error propagation
– Confidence interval

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Learning outcomes
After studying this chapter, students should be able to:
• Apply rules of significant figures in reporting results and
performing calculations.
• Perform error propagation to estimate uncertainties in
derived quantities.
• Recognize types of errors in analytical measurements
(systematic, random, gross) and explain their sources and
impacts on data quality.
• Describe the distribution of random errors, including the
normal (Gaussian) distribution, and explain its importance in
analytical chemistry.
• Calculate and interpret confidence intervals to express the
reliability of experimental results.

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Introduction
• All measurements always involve in errors and uncertainties.
• Example: Errors involved in a titration

chem.uiuc.edu
chem-ilp.net

– Difference in color of the solution of at the endpoint: caused by

experimenter.
– Difference in volume of the titrant used: caused by personal error, fail
in calibration of buret,… 4
Important terms
• Mean: X, is the numerical average:

where Xi is the ith measurement, and n is the number of

independent measurements.

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Important terms
• Median:
– Xmed is the middle value when data are ordered from the smallest to
the largest value.
– Odd number of measurements: median is the middle value.
– Even number of measurements: median is the average of the n/2 and
the (n/2) + 1 measurements, where n is the number of measurements.

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Important terms
• Precision: refers to the closeness of the results
obtained from iden cal measurement →
describes reproducibility.

• Accuracy: describes how close a single True value

measurement to the true value and is
expressed by error. Measurement

• Precision and accuracy: are both achieved

when results are close to each other and to the
true value.

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Significant figures
• Significant figures: the number of digits reported in a
measurement reflect the accuracy of the measurement and
the precision of the measurement device.

• Significant figures are all certain figures plus one extra figure
having some uncertainty.
• Example:

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Significant figures
• Rule 1: Disregard all initial zeros, all remaining digits including
terminal zeros and zeros between nonzero integers are
significant.

• Examples: Determine the number of significant figures of

a. 0.005
b. 0.030
c. 0.207
d. 92500

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Significant figures
• Rule 2: For addition and subtraction, the smallest number of
digits to the right of the decimal set the significance.
• Examples:
1.362 22.989 770
+ 3.111 + 35.453 Rule for rounding to drop
all insignificant numbers:
4.473 58.442 770 round up for digits ≥ 5,
round down for digits < 5
Not significant
58.443
Rounding up
• Exercises:
1) Rounding to 3 significant figures: 0.135 2; 0.0216 74
2) Write answer with the correct number of digits: 12.3 – 1.63 =;
1.021 + 1.63 =
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Significant figures
• Rule 3: For multiple and division, the smallest number of
significant digits determines the significance.
• Examples:

3.26 × 10-5 34.60

× 1.78 ÷ 2.4687
5.80 × 10-5 14.05

• Exercise:
Write answer with the correct number of digits: 4.34 × 9.2 = 39.928

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Significant figures
• Rule 4:
– Number of digits in mantissa of log x = number of significant figures in
x
• Example:

– Number of digits in antilog x ( 10x) = number of significant figures in

mantissa of x:
• Example:

• Exercises: find the significant figures of these numbers:

log 0.001 237 = ? ; log 3.2 = ?
antilog 4.37 = ? ; 102.600 = ?
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Errors
• Absolute error E: in the measurement of a quantity x is given
by the equation:
𝐸 𝑋 -𝑋
Where 𝑋 is the true or accepted value.
– Example: Results from 6 replicate determinations of iron in aqueous
samples of a standard solution containing 20.0 ppm iron(III ).
1st: 19.4; 2nd: 19.5; 3rd: 19.6; 4th: 19.8; 5th: 20.1; 6th: 20.3.
• Absolute error of the 5th replicate:
E = 20.1 - 20.0 = 0.1 ppm

– The sign in stating the absolute error is retained.

• Relative error Er: is a more useful quantity
𝐸𝑟 % 𝐸𝑟 100%

Example: Mean = 19.8

Relative error for the mean:
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Er = (19.8 - 20.0) x 100%/20.0 = - 1%
Errors
• Every measurement has some uncertainty, called
experimental error.
• Experimental error is classified as systematic or random.
• Systematic errors:
– Also called determinate error, arises from a flaw in equipment or the
design of an experiment. If you conduct the experiment again in
exactly the same manner, the error is reproducible.
– In principle, systematic error can be discovered and corrected.

Measured pH 7.38  0.18 unit too high

When you read a pH of

7.00, the actual pH of the
Known pH 7.20
sample is ?
www.twinklinghope.wordpress.com 14
Systematic errors
• 3 types of systematic errors:

– Instrumental errors: are caused by non ideal instrument behavior, by

faulty calibrations, or by use under inappropriate conditions.
Calibration or proper use eliminates most systematic errors of this
type.

– Method errors: arise from non-ideal chemical or physical behavior of

analytical systems. Errors inherent in a method are often difficult to
detect and are thus the most serious of the three types of systematic
error.

– Personal errors: result from the carelessness, inattention, or personal

limitations of the experimenter.

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Random errors
• Random errors:
– Also called indeterminate error, arises from uncontrolled variables in
the measurement.
– Never totally be eliminated and are often the major source of
uncertainty in a determination.
– Has an equal chance of being positive or negative.

58.? (58.2, 58.3 or 58.4)

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Gross errors
• Gross errors:
– 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.

– They are often the product of human errors.

– Example: Lost of precipitate before weighing  low result; Touching a

weighing bottle with bare hands after zero  high mass reading.

– Gross errors lead to outliers, results that appear to differ markedly

from all other data in a set of replicate measurements.

– Statistical tests can be performed to determine if a result is an outlier.

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Statistical treatment of random errors
• Accumulated effect of the individual uncertainties causes
replicate measurements to fluctuate randomly around the
mean of the set.

• Distribution of random errors:

– Example: Calibration of a 10 mL pipet with replication of 50 times.

1  ( x   )2 /2 2 : population mean

y e
 2 : standard deviation

 Replicate data from most quantitative analytical experiments

approaches that of the Gaussian curve (bell-shaped curve).
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Fundamentals of analytical chemistry, Skoog, D. A
Statistical treatment of random errors
• Statistical analysis is based on the assumption that random
errors in analytical results follow a Gaussian, or normal
distribution.
• Population is the collection of all measurements of interest,
can be real and finite or a hypothesis or concept.
∑
Mean 𝜇

• Characterizing population by taking sample.

∑ 𝑋
𝑋
𝑁
• When no systematic errors present, population mean is also the
true value.
• Probable difference between 𝑋 and 𝜇 decreases with increasing
the number of measurements made up the sample.
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Properties of Gaussian curve
• Population standard deviation : measure precision of a
population data.

∑ 𝑋 𝜇
𝜎
𝑁
𝑋 𝜇 1  z 2 /2
𝐼𝑓 𝑧 y e
𝜎  2

• Area under the Gaussian curve: gives the probability of a

measured value.
 1
1 1
area   e  ( x   )2 /2 2
dx   e  z 2 /2
dz  0.683
  2 1 2
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Fundamentals of analytical chemistry, Skoog, D. A
Properties of Gaussian curve
• Area under the Gaussian curve:
~ 68.3% of the values will lie The area under entire Gaussian curve = 1
within ±  (z = ± 1)  100 % the values making up the
population will lie within ±.

Fundamentals of analytical chemistry, Skoog, D. A

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Sample standard deviation
• Sample standard deviation s (absolute standard deviation):

∑ 𝑋 𝑋 2 ∑ 𝑑
𝑠
𝑁 1 𝑁 1
• Where 𝑋 𝑋 2 represents the deviation di of value Xi from the
mean 𝑋 .
• (N-1) is the number of degrees of freedom.
• Pooling data to increase the reliability of s: spooled is a weighted
average of individual estimates:

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Sample standard deviation
• Sample standard deviation s:
– Example:

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Sample standard deviation
• Variance (s2): can be used to describe the precision of the
data.
∑ 𝑋 𝑋 2 ∑ 𝑑
𝑠2
𝑁 1 𝑁 1
𝑠
• Relative standard deviation (RSD): 𝑅𝑆𝐷
𝑋

– The result is often expressed in ppt (part per thousand):

𝑠
𝑅𝑆𝐷 𝑖𝑛 𝑝𝑝𝑡 1000 𝑝𝑝𝑡
𝑋
– The result is also expressed in percent, coefficient of variance (CV):
𝑠
𝐶𝑉 100%
𝑋
• Spread or range (w): describes the precision of a set of
replicate results. 𝑤 𝑙𝑎𝑟𝑔𝑒𝑠𝑡 𝑣𝑎𝑙𝑢𝑒 𝑠𝑚𝑎𝑙𝑙𝑒𝑠𝑡 𝑣𝑎𝑙𝑢𝑒
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Error propagation
• Addition/subtraction:

If 𝑦 𝑎 𝑏 𝑐; then 𝑠 𝑠 𝑠 𝑠

• Example:
Standard deviation of the result:

• Multiplication/Division:

If 𝑦 𝑎 𝑏/𝑐; then
• Example:

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Error propagation
• Exponential:
If 𝑦 𝑎 ; then 𝑥 (the exponent x can be considered
free of uncertainty).

• Example:

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Error propagation
• Logarithm and antilogarithm:

𝐼𝑓 𝑦 log 𝑥 ; then 𝑠 ≅ 0.434 26

𝐼𝑓 𝑦 10 ; then 𝑙𝑛10 𝑠 ≅ 2.302 6 𝑠

• Examples:

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Confidence intervals (CI)
• Confidence interval for the mean is the range of values within
which the population mean  is expected to lie with a certain
probability.
• Example: 99% probable that the true population mean for a
set of calcium measurements lies in the interval 7.25% ±
0.15% Ca. Thus, the mean should lie in the interval from
7.10% to 7.40% Ca with 99% probability.

• 99%  confidence level % calcium (Ca)

• 7.10% - 7.40 %  confidence interval
7.40%
• 7.10%, 7.40%  confidence limits 99% chance that
the true value
7.25%
lies in this
interval
7.10%

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CI when  is known or s is a good approximation of 

𝜇 𝑋 (z comes from the area under the Gaussian curve)

– % confidence is the % area defined by ± z.

Z = ± 0.67  50 % probability that 

will fall in the interval 𝑋 0.67𝜎

– The probability that a result is outside of the confidence level is

called the significance level. 29
CI when  is known or s is a good approximation of 

• Example 1: Determine the 80% and 95% confidence intervals

for (a) the first entry (1108 mg/L glucose) and (b) the mean
value for month 1. Assume that in each part, s = 19 is a good
estimate of σ.

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CI when  is known or s is a good approximation of 

• Example 2: How many replicate measurements in month 1 are

needed to decrease the 95% confidence interval to 1100.3 ±
10.0 mg/L of glucose?

 14 measurements are needed to provide a slightly better than

95% chance that the population mean will lie within ± 10 mg/L
of the experimental mean.

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CI when  is unknown
• Use t statistical parameter t (Student’s t), which is defined in
exactly the same way as z except that s is substituted for σ.
• For a single measurement with result x:
𝑥 𝜇
𝑡
𝑠
• For the mean of N measurements:
𝑥̅ 𝜇
𝑡
𝑠/ 𝑁
• CI for the mean of N replicate measurements:
𝑡𝑠
𝐶𝐼 𝑓𝑜𝑟 𝜇 𝑥
𝑁
Note: t depends on the desired confidence level and the number of degrees
of freedom (N-1) in the calculation of s.

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CI when  is unknown

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CI when  is unknown
• Example 1: chemist obtained the following data for the
alcohol content of a sample of blood: % C2H5OH: 0.084, 0.089,
and 0.079. Calculate the 95% confidence interval for the mean
assuming:
(a) The three results obtained are the only indication of the precision of
the method

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CI when  is unknown
(b) from previous experience on hundreds of samples, we know that the
standard deviation of the method s = 0.005% C2H5OH and is a good
estimate of σ

 A sure knowledge of  (± 0.006% as compared to ± 0.012%

of unknown )can decrease the confidence interval by a
significant amount.

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