Quantitative Analysis Ch 27 Gravimetric Analysis

Classical gravi – metric

• Gravimetric – mass of analyte (weighing - measure)
• volumetric (or titrimetric) – volume of solution
containing sufficient reagent to react completely with
analyte Chemical analysis based on the determination of
Instrumental weight of a substance of known composition (the final
• Electroanalytical – properties resulting from Ox./Red. product) that is chemically related to the analyte.
behavior of analyte
• Spectroscopic – measures electromagnetic radiation
absorbed or emitted by analyte
• Chromatographic – separates a mixture into its
components
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Gravimetric Analysis Precipitation Method

• precipitation method: Dissolved analyte
converted to sparingly soluble precipitate
Ag+ + Cl- à AgCl(s)
• volatilization method: Analyte is volatilized at
suitable temperature; the volatile product is
collected and weighted
NaHCO3(aq)+H2SO4(aq)àCO2(g)+H2 O(l)+NaHSO4(aq)
CO2(g)+2NaOH(s)àNa2CO3(s)+H2 O(l)
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(1) The desired substance: completely precipitated.
"common ion" effect can be utilized:
Ag+ + Cl- AgCl(s)
excess of Cl- which is added
(2) The weighed form: known composition.
(3) The product: "pure", easily filtered.

avoid colloidal suspension, ideally,

Steps in Gravimetric Analysis Filtration produce crystals

(precipitation)
1) Dry and weigh sample
2) Dissolve sample
3) Add precipitating reagent in excess
4) Coagulate precipitate usually by heating & wait for
some time (Aging)
5) Filtration-separate precipitate from mother liquor
6) Wash precipitate Mother liquor
7) Dry and weigh to constant weight (0.2-0.3 mg)
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Particle Size & Filterability - Precipitates Mechanisms of Precipitation
Colloids – (d = 10-6 to 10 -4 mm) Two competing processes:
-invisible to naked eye (1) Nucleation
-don’t settle out of solution When a small number of
-difficult or impossible to filter ions, atoms, molecules
initially unite.
Particles – (d = 0.10 mm or greater)
-spontaneously settle out of solution (2) Particle growth
-readily filtered and washed free of impurities The 3-D growth of a
-more desirable (typically of higher purity than particle nucleus into a
colloids) 7
larger crystal 8

Particle Size & Filterability - Control Particle Size & Filterability - Control
Relative supersaturation (RSS)
RSS = (Q-S)/Q

Where Q = concentration of solute; S =

equilibrium solubility of solute

RSS can be used estimate/control the type of

precipitate that is formed:
large: nucleation, small particles (colloids)
small: particle growth, crystalline solid likely
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Techniques to promote crystal growth

Particle Size & Filterability - Control
(1) Raising the temperature (increase S).
The goal is to form crystalline precipitates so RSS
must be minimized.
(2) Adding precipitant slowly with vigorous
mixing (decrease Q).
Recall:
RSS = (Q-S)/Q = 1-S/Q (3) Keeping the volume of solution large
Q = [solute] (decrease Q).
S = solute’s Equil. Sol.
This can be done by:
Increasing S
Decreasing Q
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 Treatment of colloidal Precipitates
pH control of precipitation
(1) Increasing the electrolyte concentration
Ca2+ + C2O42- D CaC2O4 (s) •Decreasing the vol. of the counter-ion
H2C2O4 D 2 H + + C2O42- layer
•Increasing the chance for coagulation
Homogeneous Precipitation
Colloidal Particle of AgCl
The precipitant is generated slowly by a chemical
reaction.
Fe3+ + 3 HCO2- D Fe(HCO2)3⋅nH2O(s)
HCOOH+OH- D HCO2-+H2O Boundary of ionic
atmosphere
(NH2)CO + 3 H2O + heat D OH- + CO2(g)+ 2NH4+
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Treatment of colloidal Precipitates

(2) Using a volatile electrolyte
Avoid peptization
Ex. AgCl, wash with HCl. Drying precipitate at
110°C will remove HCl.
This displace the less volatile, excess counter ion.
Treatment of colloidal Precipitates
(3) Digestion and aging
Digestion: Heating the solution for about an hour after
precipirate formation. This helps to remove weakly
bound water
Aging: Storing the solution, unheated, overnight. This
allows trapped contaminates time to “work their way
out”.
Both can result in a denser precipitate that is easier to
filter.

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Representative Gravimetric Analyses

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 Advantages/Disadvantages
• Experimentally simple and elegant
• Accurate
• Precise (0.1-0.3 %)
• Macroscopic technique-requires at least
10 mg ppt to collect and weigh properly
• Time-consuming (1/2 day?)
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Calculation Calculation
• Design of experiment • % of analyte, % A
• Content Calculation
• Evaluation of the results
• %A = weight of analyte x 100
weight of sample

• weight of ppt directly obtained à%A

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Gravimetric Factor
How Do We Get %A from ppt?
• G.F. = a (FW of analyte)
• % A = weight of ppt x gravimetric factor (G.F.) x 100 b (FW of precipitate)
weight of sample

G.F. = a (FW of analyte) • Analyte ppt G.F.

b (FW of precipitate) CaO CaCO3
FeS BaSO4
• G.F. = # gms of analyte per 1 gm ppt UO2(NO3)2.6H2O U3O8
Cr2O3 Ag2CrO4

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 Gravimetric Factor Exercise
• Analyte ppt G.F. • Consider a 1.0000 g sample containing 75%
CaO CaCO3 CaO/CaCO3 potassium sulfate (FW 174.25) and 25%
FeS BaSO4 FeS/BaSO4 MSO4. The sample is dissolved and the
UO2(NO3)2 U3O8 3UO2(NO3)2/U3O8 sulfate is precipitated as BaSO4 (FW
Cr2O3 Ag2CrO4 Cr2O3/2Ag2CrO4 233.39). If the BaSO4 ppt weighs 1.4900 g,
what is the atomic weight of M 2+ in MSO4?
• ANS: Mg2+

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