Sampling and Sample Preparation

Sampling

Sampling is the process by which a sample population is reduced in size to an

amount of homogeneous material that can be conveniently handled in the
laboratory and whose composition is representative of the population

Sampling can be termed as the process by which a

representative fraction is acquired

Sampling is often the most difficult aspect of an analysis

 Sampling and Sample Preparation
Sampling
Sample size:
- The size of sample is often used to classify the type of analysis performed

- Macro analysis is used for samples of mass more than 0.1 g

- Semimicro analysis is performed on a sample in the range of 0.01 to 0.1 g

- Micro analysis is used for sample in the range 10-4 to 10-2 g

- For sample whose mass is lower than 10-4 g, the term ultramicro analysis is sometimes
used.

Sample Size Type of Analysis

> 0.1 g Macro
0.01 to 0.1 g Semimicro
0.0001 to 0.01 g Micro
< 10-4 g Ultramicro
 Sampling and Sample Preparation
Sampling
Constituent types:

Range in concentration:

Analyte level Type of constituent

1% to 100% Major

0.01% to (100 ppm) to 1% Minor

1 ppb to 100 ppm Trace

<1 ppb Ultratrace

 Sampling and Sample Preparation
Sampling
Obtaining a representative sample
The sampling process must ensure that the items chosen are representative of the
bulk of material or population. The items chosen for analysis are often called
sampling units or sampling increments.

To avoid confusion, chemists usually call the collection of sampling units or

increment the gross sample.

Gross sample is the collection of individual sampling units. It must be

representative of the whole in composition and in particle size distribution.
 Sampling and Sample Preparation
Sampling
Sampling uncertainties
- Both systematic and random errors in analytical data can be traced to
instrument, method and personal cause.
- Errors due to invalid sampling are unique in the sense that they are not
controllable by the use of blanks and standards or by closer control of
experimental variables.
- For random and independent uncertainties, the overall standard deviation (𝑠𝑜 )
for analytical measurement is related to the standard deviation of the sampling
process (𝑠𝑠 ) and so the standard deviation of the method (𝑠𝑚 ) by the
relationship:
𝑠𝑜2 = 𝑠𝑠2 + 𝑠𝑚2

This equation shows that 𝑠𝑜 is determined predominantly by the sampling

uncertainty under these conditions.

When 𝑠𝑚 < 𝑠𝑠 /3, there is no point in trying to improve the measurement precision.
Precision can be improved by taking more samples.
 Sampling and Sample Preparation
Sampling
Steps in obtaining a laboratory sample: Identify the
The laboratory sample consists of a few population
grams to at most a few hundred grams. It
may constitute as little as 1 part in 107 or 108
of the bulk material. Collect a gross
sample
For analysis in the laboratory, the gross
sample is usually reduced in size and made
homogeneous to become the laboratory
sample. Reduce the gross
sample to a laboratory
sample
 Sampling and Sample Preparation
Sampling
The goals of the sampling process are:

To obtain a mean value that is an unbiased estimate of the

population mean.
This goal can be realized only if all members of the population have
an equal probability of being included in the sample

To obtain a variance that is an unbiased estimate of the population

variance so that valid confidence limits can be found for the mean,
and various hypothesis tests can be applied. This goal can be reached
only if every possible sample is equally likely to be drawn.
 Sampling and Sample Preparation
Sampling
Sampling homogeneous solutions of liquid and gases
- For solution of liquids or gases, the gross sample can be relatively small
- Even small volume of sample will contain many more particles
- Whenever possible, the liquid or gas samples should be stirred well before
sampling to make sure that gross sample is homogeneous
- Well-mixed solutions of liquid and gases require only a very small sample
because they are homogeneous down to the molecular level
- With large volumes of solutions, mixing may impossible, it is then best to sample
several portions of container with a ‘sample thief’, a bottle that can be opened
and filled at any desired location in the solution
- With the advent of portable sensor, it has become common in recent years to
bring the laboratory to the sample instead of bringing the sample back to the
laboratory. Most sensors, however, measure only local concentrations and do
not average or sense remote concentrations
- Gases can be sampled by using a sampling bag- it is simply opened and filled
with the gas. In other cases, gases can be trapped in a liquid or adsorbed onto
the surface of a solid.
 Sampling and Sample Preparation
Sampling Steps in sampling a particulate solid

Sampling particulate solids Identify the population to be analyzed

- It is often difficult to obtain a random
sample from a bulky particulate material Randomly collect a number of (n)
- Random sampling can best be particles to give a gross sample
accomplished while the material is being
transferred Reduce particle size to gross sample
- Mechanical devices have been developed and homogenize
for handling many types of particulate
matter. Randomly collect n particle
Sampling metals and alloys
- Sample of metals and alloys are obtained
by sawing, milling, or drilling NO Is this sample of a suitable size for the
laboratory?
- A representative sample can be obtained
YES
by sawing across the piece at random
intervals and collecting the ‘sawdust’ as the Store the laboratory sample
sample
- A granular sample can often be produced Remove portions of the laboratory
by pouring the melt into distilled water. sample for analysis
 Sampling and Sample Preparation
Sample preparation
Preparing a laboratory sample
Preparing non-homogeneous solids:
- Reduce the weight of gross sample to a finely ground and homogeneous sample
- The process involves a cycle of operations that includes crushing and grinding,
sieving, mixing, and dividing the sample to reduce its weight

Automated sample handling

- Many laboratories are using automated sample handling because of their
reliability and cost effectiveness
- Automated sample handling can lead to higher throughput, higher reliability,
and lower costs than manual sampling handling
- Two different methods of automated sample handling are the batch, or discrete
approach and the continuous flow approach.
 Sampling and Sample Preparation
Sample preparation
Crushing and grinding samples
- A certain amount of crushing and grinding is usually required to decrease the
particle size of solid samples

- Crushing and grinding must be continued until the entire sample passes through
a screen of the desired mesh size

- The process often change sample composition

Factors that can cause changes in sample composition as a result of grinding:

- Heat generation can cause losses of volatile components
- Increases the surface area of the sample and thus increases its susceptibility to
reaction with the atmosphere
- Alter substantially water content of the sample
 Sampling and Sample Preparation
Sample preparation
Mixing solids sample

- It is essential that solid materials be thoroughly mixed to ensure random

distribution of the components in the analytical samples

- A common method of mixing powders involves rolling the sample on a sheet of

glazed paper. A pile of the substance is placed in the center and is mixed by
lifting one corner of the paper enough to roll the particles of the sample to the
opposite corner. This operation is repeated many times, with the four corners of
the sheet being lifted alternately

- Effective mixing of solids is also accomplished by rotating the sample for some
time in a ball mill or a twin-shell V-blender. As the blender is rotated, the sample
is split and recombined with each rotation, leading to highly efficient mixing.
 Sampling and Sample Preparation
Sample preparation
Moisture in samples

- Laboratory samples of solids often contain water that is in equilibrium with the
atmosphere
- The composition of the sample depends on the relative humidity and ambient
temperature at the time it is analyzed
- To cope with the variability in composition, it is common practice to remove
moisture from solid samples prior to weighing
- Traditionally, drying was accomplished by heating the sample in a conventional
oven or vacuum oven or by storing in a desiccator at a fixed humidity, until the
material become constant in mass
- To speed up sample drying, microwave ovens or infrared lamps can be used for
sample preparation
- An alternative to drying samples before beginning an analysis is to determine
the water content when the samples are weighed for analysis so that the results
can be corrected to a dry basis.
Steps in an analysis

An analysis involves several

steps and operations which
depend on:
•the particular problem
• your expertise
• the apparatus or
equipment available.
The analyst should be
involved in every step.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)