Introduction to Analytical Chemistry

Lecture Date: January 14th, 2008

What is Analytical Chemistry?

Analytical chemistry seeks ever improved means of
measuring the chemical composition of natural and
artificial materials
The techniques of this science are used to identify
the substances which may be present in a material
and determine the exact amounts of the identified
substances
Qualitative: provides information about the identity of
an atomic, molecular or biomolecular species
Quantitative: provides numerical information as to the
relative amounts of species
Definitions from www.acs.org

The Role of Analytical Chemistry

-Friedrich Wilhelm Ostwald
Analytical Chemistry, or the art of
recognizing different substances and
determining their constituents, takes a
prominent position among the
applications of science, since the
questions which it enables us to answer
arise wherever chemical processes are
employed for scientific or chemical
purposes.

http://www.pace.edu/dyson/academics/chemistryplv/

The Role of Analytical Chemistry

Analytical chemists work to improve the reliability of existing techniques to
meet the demands of for better chemical measurements which arise
constantly in our society
They adapt proven methodologies to new kinds of materials or to answer
new questions about their composition.
They carry out research to discover completely new principles of
measurements and are at the forefront of the utilization of major
discoveries such as lasers and microchip devices for practical purposes.
Medicine
Industry
Environmental
Food and Agriculture
Forensics
Archaeology
Space science

History of Analytical Methods

Classical methods: early years (separation of analytes) via
precipitation, extraction or distillation

Qualitative: recognized by color, boiling point, solubility, taste

Quantitative: gravimetric or titrimetric measurements
Instrumental Methods: newer, faster, more efficient
Physical properties of analytes: conductivity, electrode
potential, light emission absorption, mass to charge ratio and
fluorescence, many more

Classification of Modern Analytical Methods

Gravimetric Methods determine the mass of the analyte or some
compound chemically related to it
Volumetric Methods measure the volume of a solution containing
sufficient reagent to react completely with the analyte
Electroanalytical Methods involve the measurement of such
electrical properties as voltage, current, resistance, and quantity of
electrical charge
Spectroscopic Methods are based on the measurement of the
interaction between electromagnetic radiation and analyte atoms or
molecules, or the production of such radiation by analytes
Miscellaneous Methods include the measurement of such
quantities as mass-to-charge ratio, rate of radioactive decay, heat
of reaction, rate of reaction, sample thermal conductivity, optical
activity, and refractive index

Analytical Methodology

1. Understanding and defining the problem

2. History of the sample and background of the problem
3. Plan of action and execution
4. Analysis and reporting of results

1. Understanding and Defining

the Problem

What accuracy is required?

Is there a time (or money) limit?
How much sample is available?
How many samples are to be analyzed?
What is the concentration range of the analyte?
What components of the system will cause an
interference?
What are the physical and chemical properties
of the sample matrix? (complexity)

2. History of sample and background

of the problem
Background info can originate from many sources:
The client, competitors products
Literature searches on related systems
Sample histories:
synthetic route
how sample was collected, transported, stored
the sampling process

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

4. Analyzing and Reporting Results

No work is complete until the customer is happy!
Analytical data analysis takes many forms: statistics,
chemometrics, simulations, etc
Analytical work can result in:
peer-reviewed papers, etc
how sample was collected, transported, stored
technical reports, lab notebook records, etc...

Components of an Analytical Method

Obtain and store sample
Extract data
from sample

Pretreat and prepare sample

Perform measurement
(instrumentation)

Compare results
with standards

Covert data
into information

Apply required
statistical techniques
Verify results

Transform
information into
knowledge

After reviewing results

might be necessary
to modify and repeat
procedure

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

An Example: HPLC vs. NMR

HPLC

NMR

L,Ds

L,S,Ds

macro, micro

Ma, Mi

Ma, Mi

pure, simple mixture, complex mixture

Sm,M

P,Sm

N,D

total analysis, speciation, isotopic and mass analysis

T,S (ion)

limited

Compounds present, Polyatomic ionic species,

Functional group, Structural, MW, Physical prop

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

Review of Background Material

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

There is never actually a complete conversion of

reactants to product in a chemical reaction, there is only
a chemical equilibrium.
A chemical equilibrium state occurs when the ratio of
concentration of reactants and products is constant. An
equilibrium-constant expression is an algebraic equation
that describes the concentration relationships that exist
among reactants and products at equilibrium

aA + bB cC + dD

K = [C]c [D]d / [A]a [B]b

Chemical Equilibrium

Typical Equilibrium Constant Expressions

Dissociation of water
2H2O H3O+ + OH-

Kw = [H3O+ ][OH-]

Acid base
NH3 + H2O NH4+ + OH-

Kb = [NH4+][OH-] / [NH3]

Solubility
PbI2(s) Pb2+ + 2I-

Ksp = [Pb2+ ][I-]2

Oxidation-Reduction
IO3- + 5I- + 6H+ 3I2(aq) + 3H20

Keq = [I2]3 / [IO3-][I-]5[H+]6

Cl2(g) + 2AgI(s) 2AgCl(s) + I2 (g) Keq = pI2/ pCl2

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

Effect of Electrolyte Concentration

Reason for deviation: The presence of electrolytes results in

electrostatic interactions with other ions and the solvent
The effect is related to the number and charge of each
ion present - ionic strength ( )

= 0.5 ( [A] ZA2 + [B] ZB2 + [C]ZC2 + ..)

where Z = charge (ex. +1, -2, )

Ionic Strength: Definitions

Dissociation of an electrolyte:
MxXm xMm+ + mXx-

Ionic Strength:

= 0.5 zi2Ci

Activity coefficient:

ai = i [X]I

Debye-Huckel limiting Law relates activity coefficient

to ionic strength

log i

0.51zi2

1 3.28 i

Mean ionic activity:

a = C (mmxx) 1/(m+x)

Ionic Strength Calculations: Examples

What is the ionic strength for a 1.0 M NaCl solution?
I = 1/2(1*12 +1*12)
I=1
What is the ionic strength for a solution whose concentrations
are 1.0 M La2(SO4)3 plus 1.0 M CaCl2
for this solution the concentrations are:
[La 3+] = 2.0 M
[SO42-] = 3.0 M
[Ca 2+] = 1.0 M
[Cl -] = 2.0 M
I = 1/2 (2*32 + 3*22 + 1*22 + 2*12)
I = 18

Aqueous Solution Equilibria

Equilibria classified by reaction taking place
1) acid-base
2) oxidative-reductive
Bronsted-Lowry definitions:
acid: anything that donates a [H+] (proton donor)
base: anything that accepts a [H+] (proton acceptor)

HNO2 + H2O NO2- + H3O+

ACID
HA + H2O A- + H3O+
Ka =

[A-

] [H3

O+

] / [HA]

BASE
NH3 + H2O NH4+ + OHKb = [NH4+][OH-] / [NH3]

Strength of Acids and Bases

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

Strength of Acids and Bases

Source: http://cwx.prenhall.com/petrucci/medialib/media_portfolio/text_images/TB17_03.JPG

Amphiprotic Compounds

Amphiprotic solvents: a solvent that can act as either an

acid or base depending on the solute it is interacting
with

methanol, ethanol, and anhydrous acetic acid are all

examples of amphiprotic solvents.
NH3 + CH3OH NH4+ + CH3OCH3OH + HNO2 CH3OH2+ + NO2-

Zwitterions: an amphiprotic compound that is produced

by a simple amino acids weak acid an weak base
functional groups
Zwitterions carry both a positive charge (amino group)
and negative charge (carboxyl group)

Titrations

Definition: an analytical technique that measures

concentration of an analyte by the volumetric addition of
a reagent solution (titrant)- that reacts quantitatively with
the analyte

For titrations to be useful, the reaction must generally

be quantitative, fast and well-behaved

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

Divide by molar mass

Multiply by stoichiometric
ratio

Multiply by molar mass

Titration Curves

Strong acid - Strong base

Strong base - Weak acid

Titration Curves

Strong base - polyprotic acid

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+)

(since A- has a strong

Any added OH- reacts with the weak acid HA:

OH- (aq) + HA (aq) -> H2O + A-(aq)
steal H+ from A-)

(since OH- can

Example: if 1 mL of 0.1 N HCl solution to 100 mL water, the

pH drops from 7 to 3. If the 0.1 N HCl is added to a 0.01
M solution of 1:1 acetic acid/sodium acetate, the pH drops
only 0.09 units.

Calculating the pH of Buffered Solutions

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)

6.Find moles HCl

NaOH: HCl is 1:1
So n(NaOH) = n(HCl) = 3 x 10-3 moles at the equivalence point
Calculate concentration of HCl: M = n V
n = 3 x 10-3 mol, V = 25.0 x 10-3L
M(HCl) = 3 x 10-3 25.0 x 10-3 = 0.12M or 0.12 mol L-1

Example 2
50mL of 0.2mol L-1 NaOH neutralised 20mL of sulfuric acid. Determine the
concentration of the acid

1.Write the balanced chemical equation for the reaction

NaOH(aq) + H2SO4(aq) -----> Na2SO4(aq) + 2H2O(l)
2.Extract the relevant information from the question:
NaOH V = 50mL, M = 0.2M H2SO4 V = 20mL, M = ?
3.Check the data for consistency
NaOH V = 50 x 10-3L, M = 0.2M H2SO4 V = 20 x 10-3L, M = ?
4.Calculate moles NaOH
n(NaOH) = M x V = 0.2 x 50 x 10-3 = 0.01 mol
5.From the balanced chemical equation find the mole ratio
NaOH:H2SO4
2:1

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

Notes on Solutions and Their Concentrations

Molar Concentration or Molarity Number of moles of solute in one Liter of
solution or millimoles solute per milliliter of solution.
Analytical Molarity Total number of moles of a solute, regardless of chemical
state, in one liter of solution. It specifies a recipe for
solution preparation.
Equilibrium Molarity (Species Molarity) The molar concentration of a
particular species in a solution at equilibrium.
Percent Concentration
a. percent (w/w) = weight solute X 100%
weight solution

b.volume percent (v/v) = volume solute X 100%

volume solution
c.weight/volume percent (w/v) = weight solute, g X 100%
volume soln, mL

Some Other Important Concepts

Limit of detection (LOD): the

lowest amount (concentration or
mass) of an analyte that can be
detected at a known confidence
level
Linearity: the degree to which a
response of an analytical
detector to analyte
concentration/mass
approximates a linear function

Limit of linearity
Detector response

Slope relates to
sensitivity

LOQ
LOD
Dynamic range

Concentration

Limit of quantitation (LOQ): the range over which quantitative

measurements can be made (usually the linear range), often
defined by detector dynamic range
Selectivity: the degree to which a detector is free from
interferences (including the matrix or other analytes)

Simple Chemical Tests

While most of this class is focused on instrumental

methods, a very large number of simple chemical tests
have been developed over the past ~300 years
Examples:
Barium: solutions of barium salts yield a white precipitate with 2
N sulfuric acid. This precipitate is insoluble in hydrochloric acid
and in nitric acid. Barium salts impart a yellowish-green color to
a nonluminous flame that appears blue when viewed through
green glass.
Phosphate: With silver nitrate TS, neutral solutions of
orthophosphates yield a yellow precipitate that is soluble in 2 N
nitric acid and in 6 N ammonium hydroxide. With ammonium
molybdate TS, acidified solutions of orthophosphates yield a
yellow precipitate that is soluble in 6 N ammonium hydroxide.
Examples are from US Pharmacopeia and National Formulary USP/NF

A Colormetric Test for Mercury

A modern example of a
spot test: a test for
Hg2+ developed using
DNA and relying on the
formation of a thymidineHg2+-thymidine complex

LOD = 100 nM (20 ppb) in

aqueous solution

Linearity from the high

nanomolar to low micromolar
range

Selective for Hg2+ and

insensitive to Mg2+, Pb2+, Cd2+,
Co2+, Zn2+, Ni2+, and other
metal ions
Angew. Chem. Int. Ed., DOI: 10.1002/anie.200700269
http://pubs.acs.org/cen/news/85/i19/8519news6.html

Concentration in Parts per Million/Billion

ppm:
cppm = mass of solute X 106 ppm
mass of solution
For dilute aqueous solutions whose densities are
approximately 1.00 g/mL, 1 ppm = 1 mg/L

ppb:
cppb = mass of solute X 109 ppb
mass of solution

Density and Specific Gravity of Solutions

Density: The mass of a substance per unit volume. In SI
units, density is expressed in units of kg/L or g/mL.

Specific Gravity: The ratio of the mass of a substance to

the mass of an equal volume of water at 4 degrees
Celsius. Dimensionless (not associated with units of
measure).

Other Helpful Information

Prefixes for SI Units
gigaG
megaM
kilok
decid
centic
millim
microu
nanon
picop
femtof
attoa

109
106
103
10-1
10-2
10-3
10-6
10-9
10-12
10-15
10-18