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Analytical Methodology
3. Plan of Action
Performance Characteristics: Figures of Merit
Which analytical method should I choose? How good is the
measurement, information content
How reproducible is it? Precision
How close to the true value is it? Accuracy/Bias
How small of a difference can be measured? Sensitivity
What concentration/mass/amount/range? Dynamic Range
How much interference? Selectivity (univariate vs. multivariate)
x x
i 1
N 1
s
RSD
x
Sm
s
N
bias = - xt
s2
Sm = Sbl+ ksbl
s
CV
100 %
x
cm
Sm Sbl
m
S = mc + Sbl
Compare results
with standards
Covert data
into information
Apply required
statistical techniques
Verify results
Transform
information into
knowledge
Present information
Handbook, Settle
Techniques
Separation Techniques
Gas chromatography
High performance liquid chromatography
Ion chromatography
Super critical fluid chromatography
Capillary electrophoresis
Planar chromatography
Spectroscopic techniques
Infrared spectrometry (dispersive and fourier transform)
Raman spectrometry
Nuclear magnetic resonance
X-ray spectrometry
Atomic absorption spectrometry
Inductively coupled plasma atomic emission spectrometry
Inductively coupled plasma MS
Atomic fluorescence spectrometry
Ultraviolet/visible spectrometry (CD)
Molecular Fluorescence spectrometry
Chemiluminescence spectrometry
X-Ray Fluorescence spectrometry
More Techniques
Mass Spectrometry
Electron ionization MS
Chemical ionization MS
High resolution MS
Gas chromatography MS
Fast atom bombardment MS
HPLC MS
Laser MS
Electrochemical techniques
Amperometric technique
Voltammetric techniques
Potentiometric techniques
Conductiometric techniques
Microscopic and surface techniques
Atomic force microscopy
Scanning tunneling microscopy
Auger electron spectrometry
X-Ray photon electron spectrometry
Secondary ion MS
Technique Selection
Location of sample
bulk or surface
Physical state of sample
gas, liquid, solid, dissolved solid, dissolved gas
Amount of Sample
macro, micro, nano,
Estimated purity of sample
pure, simple mixture, complex mixture
Fate of sample
destructive, non destructive
Elemental information
total analysis, speciation, isotopic and mass analysis
Molecular information
compounds present, polyatomic ionic species,functional group,
structural, molecular weight, physical property
Analysis type
Quantitative, Qualitative
Analyte concentration
major or minor component, trace or ultra trace
NMR
L,Ds
L,S,Ds
macro, micro
Ma, Mi
Ma, Mi
Sm,M
P,Sm
N,D
T,S (ion)
limited
Cp,Io,St
Cp,Fn,St
Ql,Qt
Ql,Qt
Location of sample
bulk or surface
Physical state of sample
gas, liquid, solid, dissolved solid, dissolved gas
Amount of Sample
Estimated purity of sample
Fate of sample
destructive, non destructive
Elemental information
Molecular information
Analysis type
Quantitative, Qualitative
Chemical equilibrium
Activity coefficients
Ionic strength
Acids and bases
Titrations
Other simple chemical tests (spot tests)
Some important figures of merit
Review of a few other helpful concepts
Chemical Equilibrium
aA + bB cC + dD
Chemical Equilibrium
Kw = [H3O+ ][OH-]
Acid base
NH3 + H2O NH4+ + OH-
Kb = [NH4+][OH-] / [NH3]
Solubility
PbI2(s) Pb2+ + 2I-
Oxidation-Reduction
IO3- + 5I- + 6H+ 3I2(aq) + 3H20
Activity Coefficients
The law of mass action breaks down
in electrolytes. Why?
Ions in solution have electrostatic interactions with
other ions. Neutral solutes do not have such
interactions.
When the concentrations of ions in a solution are
greater than approximately 0.001 M, a shielding effect
occurs around ions. Cations tend to be surrounded by
nearby anions and anions tend to be surrounded by
nearby cations. This shielding effect becomes
significant at ion concentrations of 0.01 M and greater.
Doubly or triply charged ions "charge up" a solution
more than singly charged ions, so we need a standard
way to talk about charge concentration.
Activity Coefficients
Dilute solutions and concentrated solutions have slight differences and
a more precise method of calculating and defining the equilibrium
constant is needed:
ax = x [C]
IDEAL
[ ] < 10-3
in dilute solutions-- = 1
NON-IDEAL
[ ] > 10-3
<1
Ionic Strength:
= 0.5 zi2Ci
Activity coefficient:
ai = i [X]I
log i
0.51zi2
1 3.28 i
[A-
] [H3
O+
] / [HA]
BASE
NH3 + H2O NH4+ + OHKb = [NH4+][OH-] / [NH3]
Source: www.aw.com/mathews/ch02/fi2p22.htm
p-Functions
The p- value is the negative base-10 logarithm of the molar
concentration of a certain species:
pX = -log [X] = log 1/[X]
The most well known p-function is pH, the negative
logarithm of [H3O+].
pH = - log [H3O+]
pKw = pH + pOH = 14
We can also express equilibrium constants for the strength
of acids and bases in a log form
pKa = - log(Ka)
pKb = - log (Kb)
Kw = Ka * Kb
Source: http://cwx.prenhall.com/petrucci/medialib/media_portfolio/text_images/TB17_03.JPG
Amphiprotic Compounds
Titrations
Advantages
great flexibility
suitable for a wide range of analytes
manual, simple
excellent precision an accuracy
readily automated
Disadvantages
large amount of analyte required
lacks speciation (similar structure)
colorimetric -subjective
sensitive to skill of analyst
reagents unstable
Chemical Stoichiometry
Stoichiometry: The mass relationships among reacting
chemical species. The stoichiometry of a reaction is the
relationship among the number of moles of reactants
and products as shown by a balanced equation.
Mass
Moles
Moles
Mass
Titration Curves
Titration Curves
Buffer Solutions
Buffers contain a weak acid HA and its conjugate base AThe buffer resists changes in pH by reacting with any
added H+ or OH-, preventing their accumulation. How?
Any added H+ reacts with the base A-:
H+ (aq) + A- (aq) -> HA(aq)
affinity for H+)
Henderson-Hasselbach equation
Example 1
30 mL of 0.10M NaOH neutralised 25.0mL of hydrochloric acid. Determine the
concentration of the acid
1.Write the balanced chemical equation for the reaction
NaOH(aq) + HCl(aq) -----> NaCl(aq) + H2O(l)
2.Extract the relevant information from the question:
NaOH V = 30mL , M = 0.10M HCl V = 25.0mL, M = ?
3.Check the data for consistency
NaOH V = 30 x 10-3L , M = 0.10M HCl V = 25.0 x 10-3L, M = ?
4.Calculate moles NaOH
n(NaOH) = M x V = 0.10 x 30 x 10-3 = 3 x 10-3 moles
5.From the balanced chemical equation find the mole ratio
NaOH:HCl
1:1
Example 1 (continued)
Example 2
50mL of 0.2mol L-1 NaOH neutralised 20mL of sulfuric acid. Determine the
concentration of the acid
Example 2 (continued)
6.Find moles H2SO4
NaOH: H2SO4 is 2:1
So n(H2SO4) = x n(NaOH) = x 0.01 = 5 x 10-3 moles H2SO4 at the
equivalence point
7.Calculate concentration of H2SO4: M = n V
n = 5 x 10-3 mol, V = 20 x 10-3L
M(H2SO4) = 5 x 10-3 20 x 10-3 = 0.25M or 0.25 mol L-1
Limit of linearity
Detector response
Slope relates to
sensitivity
LOQ
LOD
Dynamic range
Concentration
A modern example of a
spot test: a test for
Hg2+ developed using
DNA and relying on the
formation of a thymidineHg2+-thymidine complex
ppb:
cppb = mass of solute X 109 ppb
mass of solution
109
106
103
10-1
10-2
10-3
10-6
10-9
10-12
10-15
10-18