ANALYTICAL CHEMISTRY

CHEM 3811

CHAPTERS 6 & 7

DR. AUGUSTINE OFORI AGYEMAN

Assistant professor of chemistry
Department of natural sciences
Clayton state university
 CHAPTERS 6 & 7

VOLUMENTRIC, GRAVIMETRIC
AND
COMBUSTION

ANALYSIS
 VOLUMETRIC ANALYSIS

- Analysis by volume

Titration
- Increments of a known reagent solution (the titrant) are added
to an unknown solution (the analyte) until the reaction is complete

Titrant
- Usually in the buret

Analyte
- Usually in an erlenmeyer flask
 VOLUMETRIC ANALYSIS

Common Titrations
- Acid-Base
- Oxidation-Reduction
- Complex Formation (Complexometric)
- Precipitation Reactions

Methods of Determining Analyte Consumption

- Color change
- Absorbance of light
- Sudden change in voltage or current between a pair of electrodes
 VOLUMETRIC ANALYSIS

Equivalence Point
- The quantity of titrant added is the exact amount necessary for
stoichiometric reaction with analyte

End Point
- The quantity of titrant actually measured in an experiment

- Ideal end point is the equivalence point

 VOLUMETRIC ANALYSIS

Titration Error
- The difference between end point and equivalence point

Blank Titration
- Using a solution that contains no analyte
(same volume of same solvent but without analyte)

- Blank titration is used to estimate titration error

 VOLUMETRIC ANALYSIS
Primary Standard
- Pure and dry reagent that is accurately weighed and used
directly to determine the concentration of a solution (e.g. KHP)

- Used to standardize solutions

Standardization
- Titration of a primary standard to determine the
concentration of a titrant

Standard solution
- A solution whose concentration is known
 VOLUMETRIC ANALYSIS

Direct Titration

- Titrant is added to analyte until the end point is observed

Titrant (known) + Analyte (unknown) → Product

 VOLUMETRIC ANALYSIS
Back Titration
- Two steps involved
1. A known excess of standard reagent is added to the analyte
Reagent 1 (known) + Analyte (unknown) → Product + Excess 1

2. A second standard reagent is used to titrate the excess

of the first reagent
Reagent 2 (known) + Excess 1 (unknown) → Product

Back titration is necessary when

- Excess of reagent 1 is required for complete reaction with analyte
- End point of back titration is clearer than direct
 VOLUMETRIC ANALYSIS
Solubility Product
- Ksp is the equilibrium constant for the reaction in which a solid salt
(an ionic compound) dissolves to give its constituent ions in solution

- Solid is in its standard state so is omitted from the Ksp expression

Example
PbCl2(s) ↔ Pb2+ + 2Cl-

Ksp = [Pb2+][Cl-]2 = 1.7 x 10-5

 VOLUMETRIC ANALYSIS
Solubility Product
- The solution is said to be saturated if all the solid is
capable of being dissolved

PbCl2(s) ↔ Pb2+ + 2Cl-

x0 0 0

x0 - x1 x1 2x1

If all solid dissolves

x0 - x1 = 0 or x0 = x1
 VOLUMETRIC ANALYSIS
Common Ion Effect

Supposing x2 M NaCl is added to PbCl2

PbCl2(s) ↔ Pb2+ + 2Cl-

x0 0 x2

x0 - x1 x1 2x1 + x2

Concentration of Cl- has contributions from both PbCl2 and NaCl

 VOLUMETRIC ANALYSIS
Common Ion Effect

Ksp = [Pb2+][Cl-]2 = (x1)(2x1 + x2)2

- A salt is less soluble if one of its constituent ions is already

present in the solution

Assuming 2x1 <<< x2

2x1 can be ignored
Implies Ksp = (x1)(x2)2
 VOLUMETRIC ANALYSIS
Mixtures
- In precipitation titrations of mixtures the less soluble precipitates first
(Smaller Ksp implies less soluble)

- If the difference between the Ksp values are sufficiently large,

first precipitation nearly completes before second
precipitation starts

Consider a mixture of PbI2 and PbCl2

PbI2(s) ↔ Pb2+ + 2I- Ksp = 7.9 x 10-9
(precipitates first)

PbCl2(s) ↔ Pb2+ + 2Cl- Ksp = 1.7 x 10-5

 GRAVIMETRIC ANALYSIS
- Analysis by mass

- Product should precipitate out

Gravimetric Titration
- Titrant is measured by mass

- Concentrations are expressed as moles/kg solution

- Only pipets may be used (burets are not necessary)

 GRAVIMETRIC ANALYSIS
Precipitation
- Falling out of solution

Precipitate should
- be insoluble
- be easily filtered (should have large particles)
- have known and constant composition
- be very stable to withstand heat

- Samples are heated to get rid of traces of solvent

Precipitants
- Agents that cause precipitation
 GRAVIMETRIC ANALYSIS
Crystal Growth
- Is necessary as particle sizes must be large enough for easy filtration
- Two phases exist

Nucleation
- Dissolved particles (molecules or ions) form small crystalline
aggregates capable of growing into larger particles
- Solutes are attracted and held on pre-existing surfaces (impurities)

Particle Growth
- Solute particles add to an existing aggregate to form a crystal

- Particle Growth creates larger particles than Nucleation

 GRAVIMETRIC ANALYSIS
Homogeneous Precipitation
- Precipitant is generated slowly by a chemical reaction

- Particle Growth dominates over Nucleation due to slow precipitation

- Larger particles are formed as a result

- Ionic compounds are usually precipitated in the presence of

added electrolytes

- Most gravimetric precipitations are performed in the presence

of electrolytes
 COMBUSTION ANALYSIS

- Used for the determination of mass percentages and empirical

formula of compounds

- Samples are burned in excess oxygen and the products are measured

- Typically used to measure C, H, N, S and halogens in

organic compounds
 COMBUSTION ANALYSIS
- A combustion train is usually used for analysis of compounds
containing only carbon, hydrogen, and oxygen

- A first compartment with P4O10 (or Mg(ClO4)2 or CaCl2) traps H2O

- A second compartment with NaOH (on asbestos) traps CO2

- A third compartment is a guard tube with both P4O10 and NaOH

- Guard tube prevents entry of CO2 and H2O from the atmosphere
from the reverse direction

- Masses of trapped H2O and CO2 are then determined

 COMBUSTION ANALYSIS

O2 in O2 out
sample P4O10 NaOH P4O10/NaOH

H2O trap CO2 trap Guard tube

Furnace
with catalyst
 COMBUSTION ANALYSIS

Combustion of a 0.2000-g sample of a compound made up of

only carbon, hydrogen, and oxygen yields 0.200 g H2O and
0.4880 g CO2. Calculate the mass and mass percentage of
each element present in the 0.2000-g sample.

- Convert mass H2O/CO2 to moles using molar mass

- Determine moles H/C from number of atoms and moles H2O/CO2
- Convert moles H/C to mass H/C using molar mass
- Determine mass O by subtracting total mass H and C
from mass sample
- Calculate percentages
 COMBUSTION ANALYSIS

1 mol
mol H 2 O  0.200 g x  0.0111 mol H 2 O
18.02 g

2 mol H
mol H  0.0111 mol H 2 O x  0.0222 mol H
1 mol H 2 O

1.01 g H
mass H  0.0222 mol H x  0.0224 g H
1 mol H
 COMBUSTION ANALYSIS

1 mol
mol CO 2  0.4880 g x  0.01109 mol CO 2
44.01g

1 mol C
mol C  0.01109 mol CO 2 x  0.01109 mol C
1 mol CO 2

12.01g C
mass C  0.01109 mol C x  0.1332 g C
1 mol C
 COMBUSTION ANALYSIS
Mass O = 0.2000 g sample – (0.0224 g + 0.1332 g)

= 0.0444 g O

0.0224 g
%H  x 100%  11.2 %
0.2000

0.1332 g
%C  x 100%  66.60 %
0.2000

0.0444 g
%O  x 100%  22.2 %
0.2000