ANALYTICAL CHEMISTRY

UERM MODULE 13
MT 2023
GRAVIMETRIC ANALYSIS
INTRODUCTION TYPES OF GRAVIMETRIC ANALYSIS

GRAVIMETRIC ANALYSIS 1. COMBUSTION ANALYSIS

• Common method used to determine the amount of
• A technique in which the amount of an analyte in a
carbon and hydrogen
sample is determined by converting the analyte to
• One modified method (Dumas Method) can also
some product
determine the amount of nitrogen in a sample
- Mass of product can be easily measured
• Technique is accurate and usable with a wide range
- Analyte: the compound or species to be
of compounds.
analyzed in a sample
- Often one of the first methods used to
- Overall, gravimetry sounds simple.
characterize a new compound
o Advantages - when done correctly
a. PRINCIPALS
is highly accurate (most accurate
• Sample is heated in presence of Oxygen (O2)
of all time); requires minimal
- Converts carbon in sample to CO2
equipment
- Converts hydrogen in sample to H2O
o Disadvantage - requires skilled
operator, slow.

Convert analyte into a solid, filter, weigh, calculate via a mole - Pt, CuO, PbO2, or MnO2 is used as a catalyst in
map this process
• As CO2 and H2O form, leave the sample and flow
Example:
through a series of chambers
• Determination of lead (Pb+2) in water - Chambers contain chemicals that bind one or
both of these products
Pb+ + 2Cl- → PbCl2(s) - Example:
o P4O10 can be used to absorb H2O
• By adding excess Cl- to the sample, essentially all of o Ascarite can be used to absorb CO2
the Pb+2 will precipitate as PbCl2. o Ascarite - Sodium Hydroxide Coated
Non-Fibrous Silicate
• Mass of PbCl2 is then determined.
b. APPARATUS
- used to calculate the amount of Pb+2 in original
solution • After the sample is completely burned:
- Remove P4O10 and Ascarite cartridges and weigh
• What is the %KCl in a solid if 5.1367 g of solid gives
- If C and H are present in sample, both cartridges
rise to 0.8246 g AgCl?
will increase in mass
• Amount of C and H in the original sample is
determined from:
- Knowing the amount of sample burned
- Change in weight in each cartridge
2. PRECIPITATION ANALYSIS
• Few precipitates have all of these properties, but in
most cases appropriate techniques can help
optimize these qualities
a. PRINCIPALS
• Reagent + Analyte → Solid Product (collect and
measure mass)
• Desired Properties of Solid Product
- Should be very insoluble

CABRAN | PORTUGAL 1
 ANALYTICAL CHEMISTRY
UERM MODULE 13
MT 2023
GRAVIMETRIC ANALYSIS
- Easily filterable (i.e., large crystals) • Whether crystals or colloids are obtained depends
- Very Pure on conditions used in the precipitation
- Known and constant composition d. PROCESS OF CRYSTAL GROWTH
b. SOLUBILITY • Two Phases in Crystal Growth
• The solubility of a precipitate can be decreased by: - Nucleation – molecules in solution come
- Decreasing temperature of solution together randomly and form small aggregates
- Using a different solvent
o Usually a less polar or organic solvent
(like dissolves like)

- Particle growth – addition of molecules to a

SOLUBILITY vs. pH nucleus to form a crystal

• Nucleation and Particle growth always compete for

molecules/ions being precipitated.
SOLUBILITY VS. COMMON - If nucleation is faster than particle growth:
ION EFFECT o a large number of small aggregates
occur giving colloidal suspensions
- If particle growth is faster than nucleation:
o only a few, large particles form giving
pure crystals

SOLUBILITY VS.
TEMPERATURE

• Rates of nucleation vs. particle growth depends on:

- Amount of precipitation solute present
c. FILTERABILITY - Described by a quantity known as the Relative
• Want product to be large enough to collect on filter: Supersaturation (R)
- Doesn’t clog filter
- Doesn’t pass through filter
• (ii) Best Case: Pure Crystals • If R is large,
• Worst Case: Colloidal suspension - Large relative amount of solute in solution
- Difficult to filter due to small size - Favors nucleation and colloid formation
- Tend to stay in solution indefinitely → • In gravimmetry based on precipitations, a small
suspended by Brownian motion value of R (~1.0) is desired in order to favor large
o usually 1-100 nm in size crystal growth

CABRAN | PORTUGAL 2
 ANALYTICAL CHEMISTRY
UERM MODULE 13
MT 2023
GRAVIMETRIC ANALYSIS
• Methods for Minimizing R - Impurities absorbed or trapped within pockets
1. Increase temperature of solution in the crystal
➢ increases S - Occlusion
➢ increase amount of solute that can be in - Impurities similar to the analyte or reagent
solution at equilibrium - Impurities placed in the crystal instead of
2. Add precipitating reagent (precipitant) slowly analyte
while vigorously mixing solution • Impurities are undesirable
➢ avoids local high concentrations of solution - Change the chemical composition of the
➢ avoid nucleation and colloid formation precipitate
3. Keep volume of solution large - Causes errors in the analysis
➢ keep concentration of analyte and • Ways to Minimize Impurities
precipitating reagent low 1. Keep R small
4. Control S through chemical means - large pure crystals decrease occlusions and
➢ by adjusting pH adsorbed impurities
➢ adding complexing agents 2. Digestion allowing precipitate to stand in
➢ example: precipitation of Ca2+ with C2O42- mother liquor (precipitating solution), usually
while being heated
- promotes removal of impurities from crystal
- increases size of crystals
3. Wash precipitate, redissolve the precipitate in
fresh solvent and reprecipitate
- helps decrease all types of impurities
e. HOMOGENOUS PRECIPITATION
4. Add a masking agent to solution
• Precipitating agent is generated directly in solution
- keeps impurities from precipitating, but not
by means of a chemical reaction.
analyte
- Ideal case for precipitations
• Washing Precipitates
o agent is generated uniformly
- Precipitates from ionic compounds
throughout the solution
o need electrolyte in wash solution
o excess are avoided
o keep precipitate from breaking up and
redissolving (peptization)
- Electrolyte should be volatile
o removed by drying
• As OH is produced, pH gradually increases →
-
o HNO3, HCl, NH4, NO3, etc.
precipitates a number of compounds (CaC2O4)
- Example:
f. MISCELLANEOUS NOTES ON PRECIPITATION
o AgCl(s) should not be washed with H2O,
• Most ionic compounds are precipitated in the
instead wash with dilute HNO3
presence of some added electrolyte
• Drying/Igniting Precipitates
- e.g. 0.1 M HNO3
- Many precipitates contain varying amounts of
- Allows the small nucleation aggregates to better
H2O
overcome any charge repulsion and promotes
o adsorbed from the air (i.e. hygroscopic)
particle growth
- Precipitates are dried for accurate, stable mass
• Impurities may also be present in the crystal
measurements
- Known as co-precipitation
- Precipitates are also ignited to convert to a
- Creates errors in gravimetric analysis
given chemical form
• Types of Impurities
- Impurities adsorbed to crystal surface

CABRAN | PORTUGAL 3
 ANALYTICAL CHEMISTRY
UERM MODULE 13
MT 2023
GRAVIMETRIC ANALYSIS
SCOPE OF GRAVIMETRIC ANALYSIS

1. Accurate
2. Inexpensive
• Only major equipment is balance
3. Method is more tedious than other approaches
• must carefully consider how to minimize
potential interferences

CABRAN | PORTUGAL 4