 Designing a sampling plan.

• A sampling plan is a detailed outline of which measurements

which be taken at what time, on which material, in what
manner and by whom
• A sampling plan must support the goals of an analysis.
• In a qualitative analysis the sample’s composition does not
need to be identical to that of the substance being analyzed,
provided that enough sample is taken to ensure that all
components
can be detected.
• In a quantitative analysis, however, the sample’s composition
must accurately represent the target population.
  Where to Sample the Target Population

• Sampling errors occur when a sample’s composition is not identical to

that of the population from which it is drawn.
• When the material being sampled is homogeneous, individual
samples can be taken without regard to possible sampling errors.
• The target population is however, mostly heterogeneous.
• When the target population’s heterogeneity is of concern, samples
must be acquired in a manner that ensures that determinate sampling
errors are insignificant.

Random Sampling -A sample collected at random from the target

population.
• The ideal sampling plan provides an unbiased estimate of the
target population’s properties.
• A randomly collected sample makes no assumptions about the target
population, making it the least biased approach to sampling
  Judgmental Sampling

• The opposite of random sampling is selective, or judgmental

sampling, in which we use available information about the
target population to help select samples.
• Because assumptions about the target population are
included in the sampling plan, judgmental sampling is more
biased than random sampling however, fewer samples are
required.
• Judgmental sampling is common
when we wish to limit the number of independent variables
influencing the results of an analysis.
  Systematic Sampling

• In systematic sampling the target population is

sampled at regular intervals in space or time.
  What Type of Sample to Collect

• Having known where to collect, the next step in the plan is to know
what type to collect.
• Three methods are commonly used to obtain samples: grab
sampling, composite sampling, and in situ sampling
-Grab sample -A single sample removed from the target population
• If the target population is fairly uniform in time and space, a set of
grab samples collected at random
can be used to establish its properties
• A systematic sampling using grab samples can be used to
characterize a target population whose composition varies
over time or space
 Composite sample

-A set of grab samples that are combined to form a single

sample.
-After thoroughly mixing, the composite sample is analyzed.
-Because information is lost when individual samples are
combined, it is normally desirable to analyze each grab sample
separately.
-In some situations, however, there are advantages to working
with composite samples.
-Analyzing a single composite sample instead of many individual
grab samples, provides an appreciable savings in time and cost.
-Composite sampling is also useful when a single sample cannot
supply sufficient material for an analysis
 In situ sampling

• Sampling done within the population without the

physical removal of the sample.
• An analytical sensor is placed directly in the target
population, allows continuous monitoring without
removing individual grab samples.
• E.g The pH of a solution moving through an
industrial production line can be continually
monitored by immersing a pH electrode within the
solution’s flow.
 How Much Sample to Collect

• To minimize sampling errors, a randomly collected

grab sample must be of an appropriate size.
• If the sample is too small its composition may
differ substantially from that of the target
population, resulting in a significant sampling error.
• Samples that are too large, however, may require
more time and money to collect.
•
• How much sample to get is given by

Question
 relationship between the mass of a randomly
collected grab sample

• The relationship between the mass of a

randomly collected grab sample,
m, and the percent relative standard deviation
for sampling, R, is given by
R= percent relative
standard deviation
for sampling.
  How many samples to collect
• Once the laboratory samples have been prepared, the
question that remains is how many samples should be
taken for the analysis?
• Another important consideration is the number of samples
required to achieve a desired maximum sampling error.
• If samples drawn from the target population are normally
distributed, then the following equation describes the
confidence interval for the sampling error…..
  Implementing the Sampling Plan

• After a sampling plan has been developed, it is put into action.

• Implementing a sampling plan normally involves three steps:
 Physically of the sample from its target population.
 Preserving the sample.
 Preparing the sample for analysis
• Since sampling exposes the target population to potential
contamination, the sampling device must be inert and clean.
• Once a sample is withdrawn from a target population, there is
a danger that it may undergo a chemical or physical change
• This is a serious problem since the properties of the sample will no
longer be representative of the target population.
• For this reason, samples are often preserved before transporting them to
the laboratory for analysis.
• Even when samples are analyzed in the field, preservation may still be
necessary.
• The initial sample is called the primary, or gross sample
i.e The initial sample, collected from the target population without any
processing
• In many cases the gross sample cannot be analyzed without further
treatment.
• Processing results in size reduction, transfer of
the sample into a more readily analyzable form, or to improve its
homogeneity.
  Sample Preservation

• Once removed from its target population.

• A liquid sample’s chemical composition may change as a result
of chemical, biological, or physical processes.
• Following its collection, samples are preserved by controlling
the solution’s pH and temperature, limiting its exposure to light
or to the atmosphere, or by adding a chemical preservative.
• After preserving, samples may be safely stored for later
analysis.
•
  Sample Preparation

• Most analytical methods can be applied to analytes

in a liquid or solution state.
• For this reason a gross sample of a liquid or solution
does not need additional processing to bring it into
a more suitable form for analysis.
  Sampling of Gases

• Typical examples of gaseous samples include

automobile exhaust, emissions from industrial
smokestacks, atmospheric gases, and compressed
gases.
Sample Collection
The simplest approach for collecting a gas sample
is to fill a container, such as a stainless steel
canister or a Tedlar/Teflon bag, with a portion of
the gas.
• A pump is used to pull the gas into the container, and, after
flushing the container for a predetermined time, the container is
sealed/
• This method has the advantage of collecting a more
representative sample of the gas than other collection techniques.
• Disadvantages include the tendency for some gases to adsorb to
the container’s walls, the presence of analytes at concentrations
too low to detect with accuracy and precision.
• When using a stainless steel canister many of these disadvantages
can be overcome with cryogenic cooling, which changes the
sample from a
gaseous to a liquid state.
Gas Sampling Pump (suction device)
Gas Sampling probe
  Sample Preparation
• Unlike gases and liquids, which generally require little
sample preparation, solid samples usually need some
processing before analysis.
• Many of the analytical instruments require solutions in
liquid form, thus solids must be processed.
• Reducing Particle Size- Done by combination of crushing
and grinding the gross sample. A lab sample is the
obtained
• Large particles are crushed using jaw crushers capable of
reducing particles to diameters of a few millimeters.