CHM3123 ANALYTICAL CHEMISTRY III

REVIEW ON MOLECULAR FORMULAS o The sample is taken according to a previously arranged

regular intervals in time or space
Elemental Analysis and Calculations
- QUALITATIVE CHEMICAL ANALYSIS
o To find out what types of atoms are present
- QUANTITATIVE CHEMICAL ANALYSIS
o To find out the relative numbers of each distinct type of
atom in the molecule
- MOLECULAR MASS DETERMINATION
TYPES OF SAMPLES
Quantitative and Qualitative analysis establish an Empirical
Formula for the compound. GRAB SAMPLE
 Refers to a small representative subset of a
GROSS SAMPLE larger quantity concentration or measurement
- Consists of several portions of the material to be tested that is taken at a specific time
LABORATORY SAMPLE  Most appropriate for small operating facilities
- Small portion of the sample that is analyzed with a regular substantial number of staff for
ALIQUOT continuous sample monitoring
- Measured portion of the volume of a liquid sample taken for the COMPOSITE SAMPLE
analysis  Consists of a collection of numerous
individual 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
Figure 1. The Sampling Process allows the same number of particles to be
sampled with a smaller, more manageable
Sampling is an important step in analytical chemistry as it enables combined mass
analytical chemists to have a workable size when the target • Most analytical techniques, particularly those
population to be analyzed is large used for a quantitative analysis, require that the
analyte be in solution
TYPES OF SAMPLING PLAN
Dissolution of Solid Sample
1. RANDOM SAMPLING • Distilled water is used for inorganic salts while
o Selected in a way that any portion of the material has an methanol, chloroform, or toluene, is used for
equal and known chance of being chosen organic materials
2. SELECTIVE SAMPLING
o Sample which is deliberately chosen by using a sampling • With samples that are difficult to dissolve, the
plan that screens out materials with certain first approach is usually to try digesting the
characteristics and/or selects only material with other sample with an acid or base.
relevant characteristics.
3. CONVENIENCE SAMPLING • Many digestions are now carried out in closed
o The sample sites are selected using criteria other than containers using microwave radiation as a
minimizing the sampling error source of energy for heating the solution.
4. STRATIFIED SAMPLING Microwave digestion has several important
o Lot sample is stratified or divided, and a simple random advantages including higher temperatures (200–
sample is selected from each stratum 300 °C) and pressures (40–100 bar) and
5. SYSTEMATIC SAMPLING consequently, may be accomplished in less than

“Did you ever have someone kiss you in a crowded room and every single one of your friends was making fun of you. But 15 seconds
later they were clapping too? Then what did you do?” – Swift, Taylor. “Question”, Midnights (3AM Edition), Republic Records, 2022
 CHM3123 ANALYTICAL CHEMISTRY III

30 min. In addition, the closed container

prevents the loss of volatile gases

“Did you ever have someone kiss you in a crowded room and every single one of your friends was making fun of you. But 15 seconds
later they were clapping too? Then what did you do?” – Swift, Taylor. “Question”, Midnights (3AM Edition), Republic Records, 2022
 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 submerging  maintaining the laboratory facilities
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 technique. In general, these provide
when 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
when, in fact, the concentration is below the limit
- Storage: preservatives (such as NaF for glucose) or
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

“Two headlights shine through the sleepless night, and I will get you, and get you alone. Your name has echoed through my mind
And I just think you should, think you should know” – Swift, Taylor. “Treacherous”, Red (Taylor’s Version), Republic Records, 2021
 CHM3123 ANALYTICAL CHEMISTRY III

METHOD VALIDATION

- Process of proving that an analytical method is acceptable for 7. Limit of Detection

its intended purpose o the lowest concentration of an analyte in a sample that
can be consistently detected with a stated probability
Requirements for Method Validation may include (but not (typically at 95% certainty)
limited to):
1. Sensitivity 8. Limit of Quantitation
o Capability of responding reliably and measurably to o the smallest amount or the lowest concentration of a
changes in analyte concentration substance that is possible to be determined by means
o An analytical method must have a detection limit lower of a given analytical procedure with the established
than the concentrations to be measured accuracy, precision, and uncertainty
- If a technique responds to the absolute amount of analyte in the
sample, then the signal due to the analyte is given as follows 9. Robustness
o the ability of an analytical method to remain unaffected by
SA = kACA small variations in the method parameters

Where: SA – Signal of the Analyte (with the interference) CONTROL CHARTS

KA – Sensitivity of the Analyte  It is a sequential plot that shows the statistical
CA – Concentration of the Analyte limits of variation that are permissible for the
characteristic being measured
2. Selectivity
o Means being able to distinguish the analyte from other o Control Charts are used to monitor
species  Performance on blanks
o An analytical method is specific if its signal only depends  Calibration Checks
on the analyte  Spiked Samples
- When an interferent contributes to the signal, we expand the  Stability of Results
equation to include the interferent  Comparison of work with different analysts

SA = kACA + k1C1 + k2C2 + … Common Types of Control Charts in Quality

Assessment Programs
Where: SA – Signal of the Analyte (with the interference)
KA – Sensitivity of the Analyte PROPERTY CONTROL CHART
CA – Concentration of the Analyte  Single measurements or the means for
Kn – Sensitivity of the Interference several replicate readings are recorded
Cn – Concentration of the Interference
PRECISION CONTROL CHART
3. Accuracy  Ranges or Standard Deviations are recorded
o The closeness of a result to a true value
- Ways to Demonstrate Accuracy Constructing a Property Control Chart
o Analyze a Standard Reference Material
o Compare Results from two or more different analytical  To construct the control chart, we analyze a
methods minimum of 7-15 samples while the system is
o Analyze a blank sample spiked with a known addition of under statistical control
an analyte. Sample Matric must be the same as your  The CENTER LINE (CL) of the control chart
unknown is the average of these n samples
 The more samples in the original control
4. Precision chart, the easier it is to detect when an
o Reproducibility of a result or measurement. It is the analysis is beginning to drift out of statistical
closeness of two or more measurements to each control
other.

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 r 2
might be >0.98

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

“And they called off the circus, burned the disco down. When they sent home the horses and the rodeo clowns - I'm still on that
tightrope, I'm still trying everything to get you laughing at me” – Swift, Taylor. “Mirrorball”, Folklore, Republic Records, 2020
 CHM3123 ANALYTICAL CHEMISTRY III

“And they called off the circus, burned the disco down. When they sent home the horses and the rodeo clowns - I'm still on that
tightrope, I'm still trying everything to get you laughing at me” – Swift, Taylor. “Mirrorball”, Folklore, Republic Records, 2020
 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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the damn time. 'Coz, I like you” – Swift, Taylor. “Delicate”, Reputation, Big Machine Records, 2017