CHEM367

Sept 7th, 2017

Statistics and Calibrations

Classical quantitative analysis is what was covered in analytical chemistry

The field of analytical chemistry changed very greatly with the development of the integrated
circuit, the microprocessor and the laser
o The most intense period of chance was the 1970s, when new electronic, optical and
separations capabilities opened a period of development
o The integrated circuit allowed a weak signal to be amplified and accurately measured
The new methods brought about dynamic range, sensitivity and simple, fast sample handling
The electron-capture detector made concentration ranges of ppb/ppt detectable
o Good detection for halogens
In the 1950s, ppm were the limits of detection
Low concentration things like CFC can become a hazard, so how we interpret data is very
important
o CFC aided in the hole in the ozone layer (?)
Understand the sensitivity of these measurementssee if it is actually hazardous
Analytical chemistry uses chemical principles to find out two different types of information
o Qualitative analysis: what different components exist in a sample?
o Quantitative analysis: how much of a specific component is there in a sample?
Instrumental analysis has changed the game for analytical chemistry since it is good at both
qualitative and quantitative analysis
Classical methods: qualitative analysis
o There are a whole sequence of tests
o Arguably, it is not useful anymore since all of this information can be determined much
quicker with instrumental analysis
Instrumental methods: qualitative analysis
o Use an electrospray to burn the compound then put it into a mass spectrometer to
determine what metals are present in the sample (ICP-MS)
Classical methods: quantitative analysis
o Volumetric analysis, gravimetric analysis
o All of the uncertainty comes from the chemists skill
Instrumental methods: quantitative analysis
o Can use ICP-MS to determine the qualitative information, but no quantitative
information
o To get quantitative information, you compare the signal height to standards that were
prepared
o Instrumental methods will never approach the uncertainty of classical methods
This depends on the quality of the instrument and how the experiment is set up
You should maximize the signal to noise ratio (SNR)
o This means a calibration curve will always be needed
 Classical vs instrumental methods
o Classical method: metal quantitation by EDTA titration
Very little qualitative use
Quantitation using standardized EDTA solution, can do any metal
Good for major/minor components (pph, ppt)
Cheap, easy
Will not get any information from other things in the sample, need to do tests
for each component
o Instrumental method: metal identification and quantification using plasma directed into
MS
Qualitative analysis of high caliber
Requires standards of each metal species for quantitation
Good for trace and ultratrace components (ppm, ppb, ppt)
Very expensive, complicated to use and maintain
The technique that is used to analyze the analyte depends on the matrix
Sample vs matrix
o A sample consists of an analyte, the substance of interest, and the matrix, every other
component that is not the analyte
o The matrix can have a serious effect on the accuracy of determination
o You must take all necessary precautions to prevent an interference with your
determination; matrix effects is the interference from the matrix
o This is an important consideration for choosing the best analytical method
Technique: scientific principle useful for providing compositional information
o This is the most general, like spectrophotometry
Method: distinct adaptation of a technique for a selected measurement purpose
Procedure: written directions necessary to use a method
o More general than a protocol
Protocol: set of definitive directions that must be followed, without exception, if the analytical
results are to be accepted for a given purpose
o Usually something used in a legal setting

Different methods provide a range of precision, selectivity and speed capabilities

o Range refers to what levels of concentration can be determined using the method
o Selectivity refers to the ability of a method to distinguish the analyte over other
substances present
 o Precision is related to how easily a method can distinguish small changes in
concentration (lower value is better)
Classical analysis and standards
o Gravimetry (and a few electrochemical techniques) are absolute methodsthere is no
comparison of experimental results with any chemical standards
There is no standard involved
Can get the mass of the precipitate
o In volumetric analysis, you prepare a standardized solution to use as a titrant
With known chemical formulas and stoichiometry the amount of titrant
necessary to reach equivalence point can be related to the amount of analyte
There is a comparison between the solution that was standardized and the
analyte
This means that the limitations come from the standards
Can get the volume
Testing for authenticity
o Each alcoholic beverage has its own characteristic chromatogram
o Can detect components at a low concentration
o Cannot be used to determine the concentrations of each component just based on the
height of these peaks
o The primary things in the bottle is ethanol and water, but they are not shown on the
chromatogram
o There is no way to tell what concentrations unless he has a sample of the analyte in a
pure form in which he can use it in a standard
o This makes it harder to do quantitative analysis with instrumental techniques unless
there are all of these standards available
o Must be careful making the standards
Instrumental analysis and standards
o All instrumental techniques will require the preparation of multiple standards for
quantitative analysis
o The experimental results from measurements of the standards are compared with the
same measurement using the sample
o From this comparison, the concentration of the analyte in the sample is determined
o You must have pure analyte available for the preparation of the standards
Instrumental methods: quantitative analysis
o This is known as external standards calibration, using standards that are prepared
separately from the sample
o The relationship of Signal (Sstd) and Concentration of the Standard (Cstd) must apply to
the sample
o There must be no interference from matrix components of analyte solution
Different types of errors used in statistics
o Accuracy can only be determined in comparison with a true value
This is sometimes hard/impossible, depending on the analysis
o Precision in instrumental methods is basically limited by the quality of the calibration
data
 This is only true in cases where sampling variance is minimal
o For calibration methods, we will assume that you are not making gross errors, and that
systematic errors can be identified and corrected
This also would have to be carefully monitored by using good lab procedures
o Unless told otherwise, we will assume the data would be normally distributed
Precision refers to the reproducibility of results subject to random errors and is expressed by

o Mean: =
o Absolute deviation from the mean: =

o Relative deviation from the mean: =
o Standard deviation ( ) and variance ( 2 ) for population ( > 20):
( )2
2 = lim
1

o Estimated standard deviation or standard error ( ) and estimated variance ( 2 ) for a
( )2
sample: 2 = 1

o Standard error of a mean: = as , =

Confidence limits are the limits about the experimental value within which we expect to find the
true value with a given degree of probability (usually 95%) in the absence of systematic errors
o This interval is defined by these limits is called the confidence interval:
Correct value = experimental value , where is the error interval
o When is not known and only is available from a limited number of experimental
data
Then the true value of a single measurement will be found in the interval (
is determined from a previous series of measurements):
, where =
Then the true value of an average of measurements, , will be found in the
interval
, where =
Where takes values per the T-table and is dependent not only on the desired
confidence level (CL) but also depends on the number of degrees of freedom
In this class, it is almost always 2 degrees of freedom in accordance
to linear regression calculations
Accuracy and precision for instrumental methods
o Matrix effects minimized
o Correct choice of calibration methodology
o Careful preparation of standards
o Properly selected instrument settings
o Can be precise but inaccurate
o Can be accurate but not precise
o Neither of these cases are the best