Introduction to Analytical Chemistry

Dept of Chemical Engineering

The Islamic University of Indonesia

Tutoril 01c
 Referencees:

1. R.A. Day, JR & A.L. Underwood, Analisis Kimia

Kuantitatif
2. Christian, G.D, Aanalitical Chemistry, John Wiley
and Sons, New York
3. Treadwell, F.P. And Hall, W.T, Qualitative
Analysis, John Weley and Sons, New York
4. Vogel A.I; Macro and Semi Micri Quantitative in
Organic Analysis, Longmans, Green and Co
 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
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, competitor’s 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)

N 2
Sm 
s bias =  - xt
 x   x   N
s i 1
i

N 1
s2
Sm = Sbl+ ksbl
Sm  Sbl
s CV 
s
100%
cm 
RSD  x m
x 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 Pretreat and prepare sample

from sample

Perform measurement
(instrumentation)

Compare results
with standards

Apply required
Covert data statistical techniques
into information
After reviewing results
Verify results might be necessary
to modify and repeat
Transform procedure
information into Present information
knowledge
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
Location of sample
bulk or surface B B
Physical state of sample
gas, liquid, solid, dissolved solid, dissolved gas L,Ds L,S,Ds
Amount of Sample
macro, micro Ma, Mi Ma, Mi
Estimated purity of sample
pure, simple mixture, complex mixture Sm,M P,Sm
Fate of sample
destructive, non destructive N,D N
Elemental information
total analysis, speciation, isotopic and mass analysis T,S (ion) limited
Molecular information
Compounds present, Polyatomic ionic species, Cp,Io,St Cp,Fn,St
Functional group, Structural, MW, Physical prop
Analysis type
Quantitative, Qualitative Ql,Qt Ql,Qt
 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 NON-IDEAL

[ ] < 10-3 [ ] > 10-3

in dilute solutions--  = 1 <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
 0.51zi2 
log  i 

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 BASE
HA + H2O  A- + H3O+ NH3 + H2O  NH4+ + OH-

Ka = [A- ] [H3 O+ ] / [HA] Kb = [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 = K a * K b
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+ + CH3O-
CH3OH + HNO2  CH3OH2+ + NO2-

 Zwitterions: an amphiprotic compound that is produced

by a simple amino acid’s 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 Disadvantages
great flexibility large amount of analyte required
suitable for a wide range of analytes lacks speciation (similar structure)
manual, simple colorimetric -subjective
excellent precision an accuracy sensitive to skill of analyst
readily automated 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 A -
 The 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) (since A- has a strong
affinity for H+)
– Any added OH- reacts with the weak acid HA:
 OH- (aq) + HA (aq) -> H2O + A-(aq) (since OH- can
steal H+ from A-)
 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) = ½ x n(NaOH) = ½ 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
Limit of linearity
lowest amount (concentration or

Detector response
Slope relates to
mass) of an analyte that can be sensitivity
detected at a known confidence
level LOQ
 Linearity: the degree to which a LOD
response of an analytical Dynamic range
detector to analyte
concentration/mass Concentration
approximates a linear function
 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 thymidine-
Hg2+-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

giga- G 109
mega- M 106
kilo- k 103
deci- d 10-1
centi- c 10-2
milli- m 10-3
micro- u 10-6
nano- n 10-9
pico- p 10-12
femto- f 10-15
atto- a 10-18