Unit 4 Lecture4 - Stat-1

23/08/2021
Statistics
CHEM 315 Darwin F. Reyes, RCh, MSc

Chemistry and Environmental
Analytical Science Dept., CAS, NEUST
Chemistry I
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Discussion Outline
• Statistics in analytical chemistry
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Statistics in analytical chemistry

Gaussian distribution
• Smooth, bell-shaped curve

obtained when experiments are
repeated several times.
• Take note that typically, we
perform experiments for 3-5
times, and use statistical analysis
to estimate the large set
(population).
Harris DC (2011). Quantitative Chemical Analysis (8 th ed) New York, NY: W.H. Freeman and Company
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• The arithmetic mean, —also called the average—is the sum of the
measured values divided by n, the number of measurements:
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• The standard deviation, s, measures how closely the data are
clustered about the mean. The smaller the standard deviation, the
more closely the data are clustered about the mean.
• For an infinite set of data, the mean is designated by the lowercase

Greek letter mu, μ (the population mean), and the standard
deviation is written as a lowercase Greek sigma, σ (the population
standard deviation).
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• The quantity n – 1 is called the degrees of freedom.
• The square of the standard deviation is called the variance.
• The standard deviation expressed as a percentage of the mean

value is called the relative standard deviation (RSD) or the
coefficient of variation (CV).
• Example: Find the average, standard deviation and coefficient of

variation for 821, 783, 834, and 855. (Ans. 823, 30.3, and 0.0368)
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• Student’s t is a statistical tool used most frequently to express
confidence intervals and to compare results from different
experiments.
• The confidence interval is an expression stating that the true

mean, is likely to lie within a certain distance from the measured
mean.
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Hypothesis testing
• Null hypothesis (H0)– assumes that the numerical quantities being compared
are the same → there is no significant difference
Used in comparing:
(1) Mean of an experimental data with the data with the data believed to be the
true value;
(2) Mean of an experimental data to a predicted or cutoff value;
(3) Means or standard deviations from 2 or more sets of data
Notations: μ = true value/reference data, μ0 = measurement data
Skoog DA et al. (2014). Fundamental of Analytical Chemistry (9 th ed) Belmont, CA: Brooks/Cole
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Comparison of two means: t-Test
We use a t-test to compare one set of measurements with

another to decide whether or not they are “the same.”
Case 1: Comparison of measured value to an accepted value.

Case 2: Comparison of replicate measurements.
Case 3: Comparison of values from two different methods using the
same sample.
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Case 1: Comparison of measured value to an accepted value.
• Compute the 95% confidence interval for your answer and see if
that range includes the known answer.
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Case 2: Comparison of replicate measurements
• In this case, we have two sets of measurements, each with its own uncertainty
and no “known” value. We assume that the population standard deviation (σ) for
each method is essentially the same.
• For two sets of data consisting of n1 and n2 measurements (with averages and ),
we calculate a value of t with the formula.
• If tcalculated is greater than ttable at the 95% confidence level, the two results are
considered to be different.
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Case 3. Paired t Test for Comparing Individual

Differences
• In this case, we use two methods to make single

measurements on several different samples.
• tcalc > ttable, the difference is significant
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t-Test with a spreadsheet
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F-test: Comparison of standard deviations
• The F test tells us whether two standard deviations are “significantly”

different from each other. F is the quotient of the squares of the
standard deviations:
• We always put the larger standard deviation in the numerator so

that . We test the hypothesis that s1 > s2 by using the one-tailed F
test.
• If Fcalculated > Ftable, then the difference is significant.
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Q test for Bad Data (Grubbs test)
Sometimes one datum is inconsistent with the remaining data. You

can use the Q test to help decide whether to retain or discard a
questionable datum.
Example: 12.53, 12.56, 12.47, 12.67, and 12.48.
Gcalc < Gtable, the questionable datum is retained.

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Q test for Bad Data
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Calibration curve
A calibration curve shows the response of an analytical method to
known quantities of analyte.
• dynamic range — the concentration
range over which there is a measurable
response to analyte, even if the
response is not linear.
• linear range of an analytical method is

the analyte concentration range over
which response is proportional to
concentration.
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Calibration curve
• Standard solutions – solutions with known concentration of

analyte.
• Blank solutions – solutions containing all the reagents and
solvents used in the analysis, but no deliberately added analyte.
• Unknown solutions – sample solutions to be analyzed in the
experiment.
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Calibration curve
Constructing a calibration curve
1. Prepare solutions of known

concentrations and measure using a
specific analytical procedure.
2. Subtract the average response of the
blank samples from each measurement
of response to obtain a corrected
response.
3. Make a graph of corrected response vs.
the quantity/concentration of standards.
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Calibration curve
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Calibration curve
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Calibration curve
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23/08/2021

CHEM 315 Darwin F. Reyes, RCh, MSc

• Statistics in analytical chemistry

Statistics in analytical chemistry

• Smooth, bell-shaped curve

Statistics in analytical chemistry

Statistics in analytical chemistry

• For an infinite set of data, the mean is designated by the lowercase

Statistics in analytical chemistry

• The square of the standard deviation is called the variance.

• The standard deviation expressed as a percentage of the mean

• Example: Find the average, standard deviation and coefficient of

Statistics in analytical chemistry

• The confidence interval is an expression stating that the true

Statistics in analytical chemistry

Statistics in analytical chemistry

Notations: μ = true value/reference data, μ0 = measurement data

Statistics in analytical chemistry

We use a t-test to compare one set of measurements with

Case 1: Comparison of measured value to an accepted value.

Statistics in analytical chemistry

Case 1: Comparison of measured value to an accepted value.

Statistics in analytical chemistry

Case 2: Comparison of replicate measurements

Statistics in analytical chemistry

Case 3. Paired t Test for Comparing Individual

• In this case, we use two methods to make single

• tcalc > ttable, the difference is significant

Statistics in analytical chemistry

Statistics in analytical chemistry

Statistics in analytical chemistry

• The F test tells us whether two standard deviations are “significantly”

• We always put the larger standard deviation in the numerator so

Statistics in analytical chemistry

Sometimes one datum is inconsistent with the remaining data. You

Example: 12.53, 12.56, 12.47, 12.67, and 12.48.

Gcalc < Gtable, the questionable datum is retained.

Statistics in analytical chemistry

• linear range of an analytical method is

• Standard solutions – solutions with known concentration of

Constructing a calibration curve

1. Prepare solutions of known

Constructing a calibration curve

Constructing a calibration curve

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