Analytical Chemistry at a time; s o m e p e r f o r m t h e s e p a r

 Concerned w/ the chemical characterization a t i o n a n d m e a s u r e m e n t s t ep

of matter simultaneously
 Answers two important questions: what is B. Calculation of Amount of Analyte
it(qualitative) and how much is 1. Absolute Methods - rely upon accurately
it(quantitative) known fundamental constants for
 Knowledge of the chemical composition is calculating the amount of analyte ( e.g.
important to our daily lives atomic weights )
 Agricultural, clinical, environmental, 2. Relative Methods - require comparison
forensic, manufacturing, metallurgical, and against some solution of known
pharmaceutical chemistry concentration or signal due to some
property of the solution
Types of Analysis
Qualitative analysis: C. Size of the Sample
 Deals with the identification of elements, Method Sample weight Sample
ions or compounds present in a sample volume (mcL)
 performed by selective chemical reactions Meso Greater than >100
or with the use of instrumentation 100
Quantitative analaysis: Semi-micro 10-100 50-100
 deals with the determination of how much Micro 1-10 <50
of one or more constituents is present Ultra-micro Less than 1
 a history of the sample composition will N.B
often be known or performa qualitative test Micro and Ultra-micro are often classified as
prior to performing the more difficult “TRACE ANALYSIS”. Special handling techniques
quantitative analysis and micro balances for weighing are required for
micro and ultra-micro operations.
Classification of Quantitative Methods of Analysis
A. Type of Final Measurement D. Number of 1. Complete analysis
1. Gravimetric Analysis- the analyte by constituents 2. Partial analysis
precipitation, followed by the very determined
nonselective measurement of mass (of the E. Conc. Of analyte 1. Major analyte –
precipitate) greater than 1%
2. Volumetric or Titrimetric Analysis - the 2. Minor analysis –
analyte reacts with a measured volume of 0.1% - 1%
reagent of known concentration ; a change 3. Trace analysis -
in some physical or chemical property <0.1%
signals the completion of the reaction ; 4. Ultra-trace analysis
more rapid than gravimetric analysis – a few ppm or less
3. . Instrumental Analysis - based on the F. Nature of analyte 1. Elemental analysis
measurement of a physical p r o p e r t y ( e 2. Molecular analysis
. g . an e l e c t r i c a l p r o p e r t y o r t h e
a b s o r p ti o n o f electromagnetic Steps in Analysis
radiation) ; generally more sensitive and 1. Define the Factors
selective than the classical techniques problem - What is the problem
butless precise ; usually much more –what needs to be
expensive, capital wise ; usually more rapid, found? Qualitative
may be automated and maybe and/or q u a n ti ta ti
capableofmeasuringmore than one analyte ve?
 - What will be the
information be used
for?
- Who will use it?
- When will it be
needed?
- How accurate and
precise does it have
to be?
- What is the budget?
- The analyst should
consult with the
client to plan useful
and efficient analysis,
including how to
obtain a useful
sample
2. Select a Factors
method - Sample type
- Size of sample
- Sample preparation
needed
- Conc. And range
(sensitivity needed)
- Selectivity needed
(interferences)
- Accuracy/precision
needed
- Tools/instruments
available
- Expertise/experience
- Cost
- Speed
- does it need to be
automated?
- Are methods available in
the chemical lit?
- Are standard methods
available?
3. Obtain a Factors
representativ - Sample
e sample type/homogeneity/size
- Sampling statistics/
errors
4. Prepare the Factors
sample for - Solid, liq or gas
analysis - Dissolve?
- Ash or digest?
- Chemical separation or
masking of interferences
needed?
- Need to concentrate the
analyte?
- Need to
change(derivatize) the
analyte for detection?
- Need to adjust
conditions (pH, add
reagents)?
5. Perform any - Distillation
necessary - Precipitation
chemical - Solvent extraction
separation - Solid phase extraction
- Chromatography (may
be done as part of the
measurement step)
- Electrophoresis (may be
done as part of the
measurement step)
6. Perform the Factors
measurement - Calibration
- Validation/controls/blan
k
- Replicates
7. Calculate the - Statistical analysis
results and (reliability)
reports - Report results with
limitations/accuracy
information
Errors in chemical analysis
 Mean (x) – average value for two or more
measurements
 Median (M) – middle value in a set of data
that has been arranged in the order of size;
not being unduly influenced by an outlying
value
Precision – describes the reproducibility of
measurements
- Closeness of data to other data that have been
obtained in exactly the same way
Terms for expressing the Precision
1. Standard dev
2. Variance
 3. Relative std. deviation limitations of the
4. Coeff. Of variation expermineter
5. Spread/range - Can be reduces by
experience and care of the
Accuracy – closeness of a result to its true or analyst in the physical
accepted value expressed by the error manipulations involved
- Can never be determined exactly
Detection of Systematic Method Errors
Terms for expressing the accuracy  Analysis of std. samples – analysis of std.
1. Absolutue error (E) reference materials (SRM)
2. Relative error (Er)  Independent analysis – a second independent and
reliable analytical method can be sued in parallel
Types of errors in experimental data with the method being evaluated
Indeterminate - Accidental or random errors  Blank determinations- all steps of the analysis are
errors - Errors that affect the performed in the absence of a sample; reveal
precision of measurements errors due to interfering contaminants form the
- Due to the limited ability of reagent and vessels employed in the analysis
the analyst to control or  Variation in sample size
make corrections for
external conditions
Determinate - Systematic errors
errors - Errors affect the accuracy of
results
- May be constant or variable
- Determinable and that
presumably can be either
avoided or corrected
Gross errors - Occur occasionally
- Often large and may cause
a result to be either high or
low (outliers)

Types of systematic errros

Instrument - Are caused by
errors imperfections in measuring
devices and instabilities in
their power supplies
- Eliminated by calibration
Method - Arise from non-ideal
errors chemical or physical
behavior of analytical
systems
- Often difficult to detect
thus the most serious
among systematic errors
Personal - Result from carelessness,
errors inattention or personal