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CHEM 4811
CHAPTER 1
FUNDAMENTAL CONCEPTS
WHAT IS ANALYTICAL CHEMISTRY
Characterization
- The identification of chemical compounds or elements present
in a sample (qualitative)
Qualitative Analysis
- The identification of one or more chemical species present
in a sample
Quantitative Analysis
- The determination of the exact amount of a chemical species
present in a sample
Chemical Species
- Could be an element, ion or compound (organic or inorgnic)
CHATACTERIZATION
Bulk Analysis
- Characterization of the entire sample
Example: determination of the elemental composition of a mixture
(alloys)
Surface Analysis
- Characterization of the surface of a sample
Example: finding the thickness of a thin layer on the surface
of a solid material
Volumetric Analysis
- Analysis by volume
Gravimetric Analysis
- Analysis by mass
Examples
Acid-base titrations, redox titrations, complexometric titrations,
precipitation reactions
WET CHEMICAL ANALYSIS
Nondestructive Analysis
- Useful when evidence needs to be preserved
Examples
Forensic analysis
Paintings
INSTRUMENTAL ANALYSIS
Analyte
- A substance to be measured in a given sample
Matrix
- Everything else in the sample
Interferences
- Other compounds in the sample matrix that interfere
with the measurement of the analyte
THE ANALYTICAL APPROACH
Homogeneous Sample
- Same chemical composition throughout
(steel, sugar water, juice with no pulp, alcoholic beverages)
Heterogeneous Sample
- Composition varies from region to region within the sample
(pudding with raisins, granola bars with peanuts)
Analyze/Analysis
- Applied to the sample under study
Determine/Determination
- Applied to the measurement of the analyte in the sample
Multiple Samples
- Identically prepared from another source
Replicate Samples
- Splits of sample from the same source
THE ANALYTICAL APPROACH
General Steps in Chemical Analysis
4. Sample preparation
- Convert representative material into a suitable form for analysis
THE ANALYTICAL APPROACH
General Steps in Chemical Analysis
7. Method validation
8. Documentation
DEFINING THE PROBLEM
Qualitative Analysis
Qualitative Analysis
Empirical Formula
- The simplest whole number ratios of atoms of each element
present in a molecule
Molecular Formula
- Contains the total number of atoms of each element in a
single molecule of the compound
Isomers
- Different structures with the same molecular formula
(n-butane and iso-butane)
DEFINING THE PROBLEM
Qualitative Analysis
Enantiomers
- Nonsuperimposable mirror-image isomers
- Said to be chiral
- Have the same IR, NMR, and MS
- Mostly same physical properties
(boiling-point, melting point, refractive index)
(erythrose, glyceraldehyde)
DEFINING THE PROBLEM
Qualitative Analysis
Concentration
- The quantity of analyte in a given volume or mass of sample
- Cost analysis
- Turnaround time
(time between receipt of sample and delivery of results)
DESIGNING THE ANALYTICAL METHOD
Interference
- Element or compound that respond directly to measurement
to give false analyte signal
- Signal may be enhanced or suppressed
DESIGNING THE ANALYTICAL METHOD
Fundamental Features of Method
- The blank is usually the pure solvent used for sample preparation
Reagent blank: contains all the reagents used to prepare the sample
Matrix blank: similar in chemical composition to the sample
but without the analyte
DESIGNING THE ANALYTICAL METHOD
Representative Sample
- Reflects the true value and distribution of analyte in the
original material
SAMPLING
Steps in Sampling Process
- Gross representative sample is collected from the lot
Aliquot
- Quantitative amount of a test portion of sample solution
SAMPLING
Grab samples
- Samples taken at a single point in time
Composite Samples
- Samples taken over a period of time or from different locations
SAMPLING
Gas Samples
Scrubbing
- Trapping an analyte out of the gas phase
Examples
- Passing air through activated charcoal to adsorb organic vapors
- Bubbling gas samples through a solution to absorb the analyte
Solid Samples
Samples may be
- dissolved in water (or other solvents)
- pressed into pellets
- cast into thin films
- etc.
SAMPLE PREPARATION METHODS
- Specific methods are discussed in later chapters
Extraction
Common Solvents
Hexane, xylene, methylene chloride
SAMPLE PREPARATION METHODS
Solvent Extraction
KD distributi on coefficien t
A1
A2
SAMPLE PREPARATION METHODS
Solvent Extraction
%E
A1 V1
x 100% %E
100K D
A1 V1 A2 V2 K D V2 /V1
SAMPLE PREPARATION METHODS
Solvent Extraction
Examples
Extraction of
- pesticides, PCBs, petroluem hydrocarbons from water
- fat from milk
SAMPLE PREPARATION METHODS
Analyst must
- select the required size of sample
- select the number of samples
- select the number of replicates
- obtain the required accuracy and precision
Significant Figures =
digits known with certainty + first uncertain digit
- Report all sig. figs such that only the last figure is uncertain
May be
- constant (incorrect calibration of pH meter or mass balance)
- variable (change in volume due to temperature changes)
- additive or multiplicative
ERRORS
Examples
- Limitations of reading mass balances
- Electrical noise in instruments
ERRORS
- Random errors are always associated with measurements
(x )2
The Gaussian function is f(x) ae 2 2
1
a
σ 2π
THE GAUSSIAN DISTRIBUTION
- a is the height of the curve’s peak
Point of inflection
-3σ -2σ -σ μ σ 2σ 3σ
x
SAMPLE MEAN ( x )
- Arithmetic mean of a finite number of observations
_ x i
x i 1
1
x1 x 2 x 3 ..... x N
N N
N
lim xi
μ
N
i 1 N
E abs E abs
E rel %E rel x 100%
T T
STANDARD DEVIATION
Absolute deviation (d i ) x i x
di
D _
x
di
D(%) _
x 100% D x 100%
x
STANDARD DEVIATION
Sample Standard Deviation (s)
- A measure of the width of the distribution
x
N N 2
d 2
i i x
s i 1
i 1
N 1 N 1
xi = a measured value
N = number of observations
N-1 = degrees of freedom
STANDARD DEVIATION
Standard Deviation of the mean (sm)
- Standard deviation associated with the mean
consisting of N measurements
s
sm
N
N 2
lim x i μ
σ i 1
N N
STANDARD DEVIATION
Percent Relative Standard Deviation (%RSD)
s
%RSD _
x 100
x
Variance
- Is the square of the standard deviation
- Variance = σ2 or s2
- Is a measure of precision
- Variance is additive but standard deviation is not additive
- Total variance is the sum of independent variances
QUANTIFYING RANDOM ERROR
Median
- The middle number in a series of measurements
arranged in increasing order
- The average of the two middle numbers if the
number of measurements is even
Mode
- The value that occurs the most frequently
Range
- The difference between the highest and the lowest values
QUANTIFYING RANDOM ERROR
- The Gaussian distribution and statistics are used to determine how
close the average value of measurements is to the true value
x μ for N > 20
Random error x μ
Points of inflection
-3σ -2σ -σ μ σ 2σ 3σ
x
QUANTIFYING RANDOM ERROR
Probability
- Range of measurements for ideal Gaussian distribution
µ ± 1σ 68.3
µ ± 2σ 95.5
µ ± 3σ 99.7
QUANTIFYING RANDOM ERROR
- The average measurement is reported as: mean ± standard deviation
68.3%
known as the confidence level
(CL)
-3σ -2σ -σ μ σ 2σ 3σ
x
QUANTIFYING RANDOM ERROR
x = µ ± 2σ
a
f(x)
95.5%
known as the confidence level
(CL)
-3σ -2σ -σ μ σ 2σ 3σ
x
QUANTIFYING RANDOM ERROR
x = µ ± 3σ
a
f(x)
99.7%
known as the confidence level
(CL)
-3σ -2σ -σ μ σ 2σ 3σ
x
QUANTIFYING RANDOM ERROR
Short-term Precision
- Analysis run at the same time by the same analyst using the
same instrument and same chemicals
Long-term Precision
- Compiled results over several months on a regular basis
Repeatability
- Short-term precision under same operating conditions
QUANTIFYING RANDOM ERROR
Reproducibility
- Ability of multiple laboratories to obtain same results on a
given sample
Ruggedness
- Degree of reproducibility of results by one laboratory under
different conditions (long-term precision)
Robustness (Reliability)
- Reliable accuracy and precision under small changes in condition
CONFIDENCE LIMITS
- Refers to the extremes of the confidence interval (the range)
µ = x ± zσ
CONFIDENCE LIMITS
µ = x ± zσ
If z = 1
we are 68.3% confident that x lies within ±σ of the true value
If z = 2
we are 95.5% confident that x lies within ±2σ of the true value
If z = 3
we are 99.7% confident that x lies within ±3σ of the true value
CONFIDENCE LIMITS
μ x zs m
t
x μ
s
CONFIDENCE LIMITS
_
ts
μ x
N
- Calculate t
x1 x2 N1N 2
t
s pooled N1 N 2
Degrees of freedom = N1 + N2 - 2
CONFIDENCE LIMITS
Using the t-test to Test for Systematic Error
t x μ N
s
- A known valid method is used to determine µ for a known sample
σ12
F 2
σ2
F-TEST
- Ratio should be greater than 1 (i. e. σ12 > σ22)
Detector
- Records the signal (change in the system that is related to the
magnitude of the physical parameter being measured)
Transducer (Sensor)
- Detector that converts nonelectrical signals to electrical signals
and vice versa
PERFORMING THE EXPERIMENT
Signals and Noise
- Radio stations
- Electrical motors
- Building vibrations
1. White Noise
- Two types
Thermal Noise
- Due to random motions of charge carriers (electrons)
which result in voltage fluctuations
Shot Noise
- When charge carriers cross a junction in an
electrical circuit
PERFORMING THE EXPERIMENT
Types of Noise
y = mx + b
b
x y
2
i i x i y i x i
D
D N x i2 x i
2
xi yi xiyi xi2