Exercise 0

APPLICATION OF STATISTICAL CONCEPTS IN THE DETERMINATION OF

WEIGHT VARIATION IN SAMPLES

Name: ___________________________________ Date: ______________

OBJECTIVES

1. Demonstrate proper usage of the analytical balance.

2. Gain an understanding of some concepts of statistical analysis.
3. Apply statistical concepts in analytical chemistry

INTRODUCTION

Analytical chemistry depends on reliable measurements to provide useful data for problem
solving. These data are evaluated with respect to accuracy and precision. The optimum
technique to achieve these performance parameters is to carry out replicate measurements.
Various statistical parameters can serve as tools to provide quantitative measures of data
reliability.

Sample & Population

In statistics, population refers to an infinite number of results that could be collected over an
infinite period of time, while a statistical sample is only a subset of a population of data. In the
absence of determinate errors, the population mean (μ) is considered to be the true value. In
contrast, the sample mean (𝑋̅), is the mean of a limited sample drawn from a population data
and usually gives an estimate of μ. The precision of replicate measurements of a population is
expressed in terms of the population standard deviation (σ), which is approximated by the
sample standard deviation (𝑠).

Measures of Central Tendency

Measures of central tendency describes the location of the middle or the center of a distribution.
The definition of middle or center is purposely left somewhat vague so that the term central
tendency can be applied to a variety of measures.

1. Mean

One of the most common measures of central tendency is the mean or average, defined
as

∑ 𝑋𝑖 (𝑋1 + 𝑋2 + 𝑋3 + ⋯ 𝑋𝑛 )
𝑋̅ = =
𝑛 𝑛

where 𝑋𝑖 represents the individual values of 𝑋 making up a set of 𝑛 replicate

measurements. The value of 𝑋̅ gives an estimate of the value of dispersion. The quality
of reliability of this estimate increases with 𝑛 and when determinate errors are absent,
𝑋̅ approaches the true value of the population mean μ.
 2. Median

The median is the middle value in a set of data that has been arranged in increasing or
decreasing order. The median is used advantageously when a set of data contains an
outlier, a result that differs significantly from the rest of the data in the set. For an odd
number of results, the median can be evaluated directly. For an even number of results,
the average of the middle pair is used.

Measures of Precision

Precision describes the agreement between two or more measurements that have been made in
exactly the same way. An ideal measure of precision must have the following attributes: (1) it
must be independent of sample size; (2) it must be useful in quantitative comparisons of
different data sets; and (3) the experiments must be able to combine different sets of data,
regardless of size, to obtain better estimates of precision.

1. Average Deviation

The scatter in a set of measurements may be estimated by the average deviation (𝑑̅). It
is the average of the absolute individual deviations from the mean:

∑|𝑑𝑖 | (|𝑋1 − 𝑋̅| + |𝑋2 − 𝑋̅|+. . . |𝑋𝑛 − 𝑋̅|)

𝑑̅ = =
𝑛 𝑛

2. Variance

The variance (𝑠 2 ) is a more statistically useful measure of the scatter particularly for
random errors:
∑(𝑋𝑖 − 𝑋̅)2
𝑠2 =
𝑛−1

Note that for large values of 𝑛, the number of degrees of freedom 𝑛 − 1 approaches 𝑛.

3. Standard Deviation

The sample standard deviation (𝑠) is just the square root of the variance:
∑(𝑋𝑖 − 𝑋̅)2
𝑠=√
𝑛−1

For a population, the standard deviation (σ) is given by:

∑(𝑋𝑖 − μ)2
𝜎=√
𝑛
4. Relative Standard Deviation

Standard deviation is frequently quoted in relative rather than absolute terms. Relative
standard deviation is often expressed in terms of parts per thousand (ppt) and is given
by:
𝑠
𝑅𝑆𝐷 = × 1,000 𝑝𝑝𝑡
𝑋̅

5. Coefficient of Variation

The coefficient of variation (CV) is the relative standard deviation expressed in %:

𝑠
𝐶𝑉 = × 100%
𝑋̅

6. Pooled Standard Deviation

When several small sets have the same sources of indeterminate error (i.e. the same
type of measurement but different samples), the standard deviations of the individual
data sets may be pooled to more accurately determine the standard deviation of the
entire analysis. Pooled standard deviation (spooled) is given by:
̅̅̅1 )2 + ∑(𝑋𝑗 − 𝑋
∑(𝑋𝑖 − 𝑋 ̅̅̅2 )2 + ∑(𝑋𝑘 − 𝑋
̅̅̅3 )2 + ⋯
𝑠𝑝𝑜𝑜𝑙𝑒𝑑 = √
𝑛1 + 𝑛2 + 𝑛3 +. . . −𝑛𝑠

where 𝑛1 is the number of data in the 1st data set, 𝑛2 is the number of data in the 2nd
data set, and so forth. The term 𝑛𝑠 is the number of data sets being pooled.

For example, the pooled standard deviation of two data sets is:
̅̅̅1 )2 + ∑(𝑋𝑗 − 𝑋
∑(𝑋𝑖 − 𝑋 ̅̅̅2 )2
𝑠𝑝𝑜𝑜𝑙𝑒𝑑 = √
𝑛1 + 𝑛2 − 2

7. Range

Range or spread is the difference between the highest and lowest values in a set of
measurements. For small groups (𝑛 ≥ 3), the range is accurate enough for practical
purposes.
𝑅 = 𝑋𝑚𝑎𝑥 − 𝑋𝑚𝑖𝑛

8. Relative Range

The range may also be expressed in relative terms:

𝑅
𝑅𝑅 = × 100%
𝑋̅
Measures of Accuracy

Accuracy indicates the closeness of a measurement to its true value or accepted value and is
expressed by the error. These errors may be reported in either absolute or relative terms.

1. Absolute Error

An absolute error (𝐸) may be defined as the difference between the observed value (𝑋𝑖 )
and the true value (𝑋𝑡 ):

E = 𝑋𝑖 − 𝑋𝑡

2. Relative Error

To relate the absolute error to the size of the measured quantity, a relative value is often
used. Relative error (𝐸𝑟 ) is defined as the absolute error divided by the true value.
Experimentally, the true value is taken as the mean or average value.

𝑋𝑖 − 𝑋𝑡
𝐸𝑟 = × 100%
𝑋𝑡

Confidence Limits

The mean of a set of measurements is generally used as the best available approximation of the
true value. The probability that the mean value for an infinite number of measurements lies
within some range of the measured average can be estimated from the standard deviation 𝑠 of
the individual measurement. Such a range is expressed in terms of the confidence limit or
confidence interval (CI). The confidence limit or interval may be said to represent a certain risk
or probability that the true value lies within the limits:

𝑡𝑠
𝐶𝐼 = 𝑋̅ ±
√𝑛

In the above equation, 𝑡 is the tabulated value for a given number of measurements 𝑛:

Table 1. Values of t for Various Levels of Probability

n-1 1 2 3 4 5 6 7 8 9 10
t90% 6.31 2.92 2.35 2.13 2.02 1.94 1.90 1.86 1.83 1.81
t95% 12.7 4.30 3.18 2.78 2.57 2.45 2.36 2.31 2.26 2.23
t99% 63.7 9.92 5.84 4.60 4.03 3.71 3.50 3.36 3.25 3.17

The value of 𝑛 − 1 denotes the degrees of freedom in the system and is used in the calculations
of confidence limits of the average for a set of values.

The 95% confidence level incorporates about two standard deviation units and is often used in
estimates of validity of analytical measurements. Remember that the use of confidence limits
is valid only when determinate errors are absent.
Q-test

The best test available for objectively handling data rejection when dealing with a small
number of observations is the Q-test:
|𝑋𝑞 − 𝑋𝑛 |
𝑄𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡𝑎𝑙 =
𝑅

where 𝑋𝑞 is the questionable result or suspect value, 𝑋𝑛 is the value numerically closest to the
suspect value, and 𝑅 is the range of the data set.

In calculating averages and standard deviations, the suspect value should be rejected if 𝑄𝑒𝑥𝑝
exceeds the tabulated Q value (𝑄𝑡𝑎𝑏 ), otherwise it should be accepted. A table of Q values is
given below for different sample sizes 𝑛 and confidence levels:

Table 2. Critical values for the Rejection Quotient, Q

N 3 4 5 6 7 8 9 10
Q90% 0.941 0.765 0.642 0.560 0.507 0.468 0.437 0.412
Q95% 0.970 0.829 0.710 0.625 0.568 0.526 0.493 0.466
Q99% 0.994 0.926 0.821 0.740 0.680 0.634 0.598 0.568

Criteria for data rejection are not applied to medians. Medians are taken directly from the entire
set of data. Rejection of outliers is only carried out with the basic assumption that the
population data follows normal distribution. However, when dealing with a data set with 𝑁 <
50, normal distribution is difficult to establish. Therefore, the use of such test for outliers
should be used with utmost care.
MATERIALS/GLASSWARE/EQUIPMENT

10 x 1-peso coins
Watch glass
Forceps
Analytical balance

PROCEDURE

1. Prepare 10 samples. Handle with forceps to ensure that there will be no fingerprints on
the samples. Use a clean, dry watch glass as a sample container.
2. Following the procedure for proper use of the analytical balance, take the weights of
each sample.
3. Record all the weights of the samples in your data sheet.

CALCULATIONS
1. Perform Q-test (at 95% confidence level) for the highest and lowest values of your data set.
2. After removing outliers (if any), calculate the following statistical parameters for your data
set:
a. Mean
b. Standard deviation
c. RSD (ppt)
d. Range
e. Relative range (%)
f. Confidence interval (at 95% level)
g. Pooled standard deviation (gather data from at least two other groups)

POST-LAB QUESTIONS
1. Differentiate the 3 types of experimental errors and give examples for each type.
2. Describe the Gaussian or normal distribution. What are the requirements for a data set
to have a normal distribution?
3. What is the rationale of using forceps/crucible tongs in handling the samples?
4. Discuss the significance of the following terms:
a. Standard deviation
b. Confidence limits
c. Q-test
d. Pooled standard deviation
5. How does your group’s sample mean compare to those obtained from other groups?
 Exercise 0
APPLICATION OF STATISTICAL CONCEPTS IN THE DETERMINATION OF
WEIGHT VARIATION IN SAMPLES

Name: ___________________________________ Date: ________________

Groupmates: ______________________________ Section: ______________
Groupmates: ______________________________

Data and Results

Sample
Data from your Group Data from Other Groups
No.
1 ± ± ±
2 ± ± ±
3 ± ± ±
4 ± ± ±
5 ± ± ±
6 ± ± ±
7 ± ± ±
8 ± ± ±
9 ± ± ±
10 ± ± ±
Mean
SD