CHM3123 ANALYTICAL CHEMISTRY III

TERMINOLOGIES ON SAMPLING TECHNIQUES

Sampling TYPES OF SAMPLES
- Process of obtaining a portion of a material that will represent
the subject under study GRAB SAMPLE
- Process of obtaining a representative sample ▪ Refers to a small representative subset of a
larger quantity concentration or measurement
GROSS SAMPLE that is taken at a specific time
- Consists of several portions of the material to be tested ▪ Most appropriate for small operating facilities
LABORATORY SAMPLE with a regular substantial number of staff for
- Small portion of the sample that is analyzed continuous sample monitoring
ALIQUOT COMPOSITE SAMPLE
- Measured portion of the volume of a liquid sample taken for the ▪ Consists of a collection of numerous individual
analysis discrete samples taken at regular intervals
over a period, usually 24 hrs.
-
Requirements of Good Sampling Methods
▪ Lot Inspection
▪ Suitability of Sampling Devices
▪ Suitable Containers
▪ Maintenance and Integrity of Sample and
Associated Records

SAMPLING PLANS FOR SOLIDS

Sample Preservation
• Samples stored at reduced temperatures are less
prone to biodegradation and the loss of volatile
material
• The loss of volatile material is minimized by
ensuring that the sample completely fills its
container without leaving a headspace where
gases can collect

Sample Preparation
• Reducing the sample’s average particle size
allows the same number of particles to be
Figure 1. The Sampling Process sampled with a smaller, more manageable
combined mass
Sampling is an important step in analytical chemistry as it enables • Most analytical techniques, particularly those
analytical chemists to have a workable size when the target used for a quantitative analysis, require that the
population to be analyzed is large analyte be in solution

TYPES OF SAMPLING PLAN Dissolution of Solid Sample

• Distilled water is used for inorganic salts while
1. RANDOM SAMPLING methanol, chloroform, or toluene, is used for
o Selected in a way that any portion of the material has organic materials
an equal and known chance of being chosen
2. SELECTIVE SAMPLING • With samples that are difficult to dissolve, the first
o Sample which is deliberately chosen by using a approach is usually to try digesting the sample
sampling plan that screens out materials with certain with an acid or base.
characteristics and/or selects only material with other
relevant characteristics. • Many digestions are now carried out in closed
3. CONVENIENCE SAMPLING containers using microwave radiation as a source
o The sample sites are selected using criteria other than of energy for heating the solution. Microwave
minimizing the sampling error digestion has several important advantages
4. STRATIFIED SAMPLING including higher temperatures (200–300 °C) and
o Lot sample is stratified or divided, and a simple random pressures (40–100 bar) and consequently, may
sample is selected from each stratum be accomplished in less than 30 min. In addition,
5. SYSTEMATIC SAMPLING the closed container prevents the loss of volatile
o The sample is taken according to a previously arranged gases
regular intervals in time or space

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 CHM3123 ANALYTICAL CHEMISTRY III

SAMPLING PLANS FOR LIQUIDS QUALITY ASSURANCE IN ANALYTICAL CHEMISTRY

Sample Collection Quality – totality of characteristics of an entity that bear

on its ability to satisfy stated and implied needs
- Homogeneous solutions are easily sampled by siphoning,
decanting, or by using a pipet or syringe Quality System – organizational structure, procedures,
processes, and resources needed to implement quality
- Manual shaking is often sufficient to ensure homogeneity management

- Grab sample is often sufficient Quality Management – all activities of the overall
management function that determine the quality policy,
- If natural diffusion is slow, shaking/stirring is done before objectives, and responsibilities, and implement them by
sampling means such as quality planning, quality control and
assurance, and quality improvement within the quality
- Large stationary liquid can be sampled using thief sampler system

SAMPLING PLANS FOR NATURAL WATERS Good Laboratory Practices (GLP)

▪ Describe the general laboratory operations
Sample Containers that we must follow in any analysis

- Glass containers are always used when collecting samples for • properly recording data and
the analysis of pesticides, oil and grease, and organics. maintaining records
- Since glass surfaces easily adsorb metal ions, plastic bottles • using chain-of-custody forms for
are preferred when collecting sample for the analysis of trace samples
metals. • specifying and purifying chemical
reagents
o The chemical composition of surface waters, such as • preparing commonly used reagents
streams, rivers, lakes, estuaries, and oceans, is • cleaning and calibrating glassware
influenced by flow rate and depth. • training laboratory personnel
o Grab samples are conveniently collected by • maintaining the laboratory facilities
submerging a capped bottle below the surface and
removing the cap. Good Measurement Practices
o The air–water interface, which may be enriched with ▪ Describe those operations specific to a
heavy metals or contaminated with oil, is avoided when technique. In general, these provide
collecting the sample. instructions for maintaining, calibrating, and
o Wells used for collecting groundwater samples must be using equipment, and instrumentation
purged until the water’s temperature, pH, or specific
conductance are constant. QUALITY ASSESSMENT
- process of collecting data to show that analytical
SAMPLING OF BIOLOGICAL FLUIDS procedures are operating within specified limits, verifying
that the final results meet the objectives.
- Timing for biological samples is important (e.g., blood
composition changes before and after meal, sampling after 12h Methods of Quality Assessment
fasting is often recommended ➢ Internal Methods of Quality Assessment
- In case of blood, a grab sample can be done. Syringes are o Prescriptive Approach
used to collect blood samples. o Performance-Based Approach
- Blood can be analyzed as whole blood or separated into serum ➢ External Methods of Quality Assessment
and plasma o Proficiency Testing
▪ Serum: fluid separated from clotted blood.
Serum does not clot.
FALSE CONCLUSIONS
▪ Plasma: fluid separated from unclotted blood,
contains fibrinogens
False Positive – concentration exceeds the legal limit
- Storage: preservatives (such as NaF for glucose) or when, in fact, the concentration is below the limit
anticoagulant (Heparin) are used
False Negative – concentration is below the limit when it
is actually above the limit
- Vacutainers (evacuated tubes with rubber caps) are used to
collect blood samples

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 CHM3123 ANALYTICAL CHEMISTRY III

METHOD VALIDATION 7. Limit of Detection

o the lowest concentration of an analyte in a sample that
- Process of proving that an analytical method is acceptable for its can be consistently detected with a stated probability
intended purpose (typically at 95% certainty)

Requirements for Method Validation may include (but not limited 8. Limit of Quantitation
to): o the smallest amount or the lowest concentration of a
1. Sensitivity substance that is possible to be determined by means
o Capability of responding reliably and measurably to of a given analytical procedure with the established
changes in analyte concentration accuracy, precision, and uncertainty
o An analytical method must have a detection limit lower
than the concentrations to be measured 9. Robustness
- If a technique responds to the absolute amount of analyte in the o the ability of an analytical method to remain unaffected
sample, then the signal due to the analyte is given as follows by small variations in the method parameters

SA = kACA CONTROL CHARTS

▪ It is a sequential plot that shows the statistical
Where: SA – Signal of the Analyte (with the interference) limits of variation that are permissible for the
KA – Sensitivity of the Analyte characteristic being measured
CA – Concentration of the Analyte
o Control Charts are used to monitor
2. Selectivity ➢ Performance on blanks
o Means being able to distinguish the analyte from other ➢ Calibration Checks
species ➢ Spiked Samples
o An analytical method is specific if its signal only ➢ Stability of Results
depends on the analyte ➢ Comparison of work with different analysts
- When an interferent contributes to the signal, we expand the
equation to include the interferent Common Types of Control Charts in Quality
Assessment Programs
SA = kACA + k1C1 + k2C2 + …
PROPERTY CONTROL CHART
Where: SA – Signal of the Analyte (with the interference) ▪ Single measurements or the means for
KA – Sensitivity of the Analyte several replicate readings are recorded
CA – Concentration of the Analyte
Kn – Sensitivity of the Interference PRECISION CONTROL CHART
Cn – Concentration of the Interference ▪ Ranges or Standard Deviations are recorded

3. Accuracy Constructing a Property Control Chart

o The closeness of a result to a true value
- Ways to Demonstrate Accuracy ▪ To construct the control chart, we analyze a
o Analyze a Standard Reference Material minimum of 7-15 samples while the system is
o Compare Results from two or more different analytical under statistical control
methods ▪ The CENTER LINE (CL) of the control chart is
o Analyze a blank sample spiked with a known addition the average of these n samples
of an analyte. Sample Matric must be the same as your ▪ The more samples in the original control chart,
unknown the easier it is to detect when an analysis is
beginning to drift out of statistical control
4. Precision
o Reproducibility of a result or measurement. It is the
closeness of two or more measurements to each other.
f
5. Linearity
o Measures how well a calibration curve follows a straight
line
o A value of r2 above 0.995 or, perhaps, 0.999, is deemed
a good fit for many purposes
o For the assay of impurities, an acceptable value of r2
might be >0.98

6. Range
o Concentration range over which linearity, accuracy, and
precision meet specifications for analytical method

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 CHM3123 ANALYTICAL CHEMISTRY III

Constructing a Precision Control Chart

▪ To construct the control chart, we analyze a minimum of 15-

20 samples while the system is under statistical control
▪ The CENTER LINE (CL) of the control chart is the average of
these n samples

INTERPRETING CONTROL CHARTS

- The purpose of a control chart is to determine if an analysis is in

a state of statistical control. It is done by examining the location
of individual results relative to the warning limits and the control
limits, and by examining the distribution of results around the
central line.
- When a result exceeds a control limit, the most likely explanation
is a systematic error in the analysis or a loss of precision. In
either case, we assume that the analysis no longer is in a state
of statistical control.

NELSON RULES
- method in process control of determining whether some
measured variable is out of control (unpredictable versus
consistent).

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