Gravimetric Analysis

By: Dr. O. Rajabi (Pharm.D.- Ph.D.)

Associate Professor of Chemistry

gravi metric
(weighing measure)
Definition:
a precipitation or volatilization
method based on the determination of
weight of a substance of known
composition that is chemically related
to the analyte
analyte

- chemical element or
compound of interest

 Reaction:

aA + rR -----> AaRr ppt

where:
a is # of moles of analyte A
r is # of moles of reagent R
AaRr is a pure, insoluble precipitate
which we can dry and weigh or ignite
to convert to something we can weigh
ppt=precipitate

1914

Nobel Prize to
T.W.Richards (Harvard
University) for the atomic
weights of Ag, Cl, and N

Richards

and his group

determined atomic weights
of 55 of the 92 known
elements using gravimetry

T.W.Richards:
Every

substance must be
assumed to be impure, every
reaction must be assumed to be
incomplete, every method of
measurement must be assumed to
contain some constant error, until
proof to the contrary can be
obtained.

7 Steps in Gravimetric
Analysis
Dry

and weigh sample

Dissolve sample
Add precipitating reagent in excess
Coagulate precipitate usually by heating
Filtration-separate ppt from mother
liquor
Wash precipitate (peptization)
Dry and weigh to constant weight

Precipitation:
Dissolve

sample
Add ppting
reagent
Filter
Dry
Weigh

dissolved
components
sample

precipitating agent

Suction Filtration
Filter

flask
Buchner funnel
Filter paper
Glass frit
Filter adapter
Heavy-walled
rubber tubing
Water aspirator

 Mother

liquor

Identify insoluble form

Two considerations:

Minimize errors due to limited precipitate

solubility
Minimize errors due to precipitation process

Finite solubility of precipitate

a.

ideally, Ksp = 0 (i.e., completely insoluble)

o

Some come close:

~10-50 for Ag2S

~10-38 for Fe(OH)3

For AgCl, Ksp = 1.78 x 10-10

For example:
what would be the % error introduced in gravimetric
analysis by the solubility of AgCl?
Ksp =[Ag+][Cl-]
S =[Ag+] =[Cl-]

S = Ksp =1.33x10-5 M

For a 0.1000 g AgCl precipitate in 200 ml H 2O:

0.200L

1.33x10-5 molAgCl 143.32gAgCl

-4 gAgCl
=
3.824x10

1L

1molAgCl

3.824x10-4 g
So, % error :
x 100 = 0.38%
0.1000g

Note: Error is independent of mass of precipitate,

relative error will decrease as precipitate mass increases
(i.e., 0.038% error for 1.000 g AgCl)

b.

Precipitation process

ideally, wed like a precipitate that forms quickly. Th

implies:

Large, pure crystals

Low solubility
Easily filtered
Easily washed

How does precipitation occur?

1. As Ksp is exceeded, solution becomes

supersaturated
2. At some point nucleation begins
3. At the same time, crystal growth begins

Two points to remember:

1. Crystal

growth is independent of degree of supersaturation

2. Nucleation increases with degree of supersaturation

Minimization of supersaturation will produce the largest

particles

Two

particle size classes

Colloids
very

small
difficult to handle experimentally

Crystals
large

(~ 10-1 mm)
easily and rapidly filtered
high purity

 What

affects degree of supersaturation?

Ksp
Temperature
solubility

as T

Reagent addition speed

slower

addition gives
precipitation a chance
to begin at lower
supersaturation levels

Solution concentration
low

reagent concentration
equals low supersaturation

But, even with the above precautions, we will often

obtain colloid instead of a crystal!

Keys to successful colloid precipitation:

1.
2.

Add precipitant slowly and in slight excess

Digest precipitate (Heat, stir, sit)

What about crystalline precipitate?

Similar to colloids:
1.
2.
3.
4.

Dilute solution
Slow precipitant addition
Elevated temperature
Heat unstirred

Contaminants can escape from crystal lattice

Increase crystal bridges

 Particle

Size / Filterability

produce particles large enough to be

'caught
ideally, produce crystals
avoid colloidal suspension
particle size = 1 - 100 nm

Precipitate Formation
crystallization

nucleation:
particles join to produce aggregates
crystal growth
aggregate grows and 'fall out' of solution

We want a few big chunks of precipitate!

supersaturation:
more solute than should be present in solution
relative supersaturation:
a measure of supersaturation, (Q-S)/S
Q = actual solute concentration
S = equilibrium solute concentration

Controlling Precipitation
Increase

Increase temperature
Decrease

Dilute solution
Well mixed (stirring)

What Do We Get Out of

Gravimetry?
%

of analyte, % A

%A

= weight of analyte
weight of sample

x 100

How Do We Get %A?

% A = weight of ppt x gravimetric factor (G.F.) x 100

weight of sample

G.F. =

G.F.

ppt

a FW[analyte]
b FW[precipitate]

= # gms of analyte per 1 gm

Gravimetric Factor
X

apples + Y sugar = Z apple pies

What

is this relationship in
chemistry?

The Gravimetric Factor

G.F.

Analyte

a FW[analyte]
b FW[precipitate]

ppt
CaO
CaCO3
FeS
BaSO4
UO2(NO3)2.6H2O U3O8
Cr2O3
Ag2CrO4

G.F.

 Analyte

ppt G.F.
CaO
CaCO3 CaO/CaCO3
FeS
BaSO4 FeS/BaSO4
UO2(NO3)2 U3O8
3UO2(NO3)2/U3O8
Cr2O3 Ag2CrO4 Cr2O3/2Ag2CrO4

Problem
Consider

a 1.0000 g sample
containing 75% potassium sulfate
(FW 174.25) and 25% MSO4. The
sample is dissolved and the sulfate is
precipated as BaSO4 (FW 233.39). If
the BaSO4 ppt weighs 1.4900, what is
the atomic weight of M2+ in MSO4?
ANS: Mg2+

Answer
The

hard part is setting up the

correct equation (good
stoichiometry skills are essential
here!):

0.75 * 233.39 0.25 * 233.39

1.4900

174.25
x 96.06

Rearranging

and solving:
2
58.3475
0.4855
; x 24.12( Mg )
x 96.06

Problem
A

mixture of mercurous chloride (FW

472.09) and mercurous bromide (FW
560.99) weighs 2.00 g. The mixture is
quantitatively reduced to mercury metal
(At wt 200.59) which weighs 1.50 g.
Calculate the % mercurous chloride and
mercurous bromide in the original
mixture.
ANS: 0.5182 g

Answer
Again,

important to set up correct

equation:

2 * 200.59 * x 2 * 200.59 2 x
1.50

472.09
560.99

Rearranging

and solving:

0.8498 0.7151 2 x 1.50

x 0.5182 g

Homogeneous Precipitation

(NH2)CO + 3 H2O + heat

HCOOH + OH- + CO2 + 2 NH4+

High Electrolyte
Concentration
to Aid Precipitation

Excess charge on colloid creates

ionic atmosphere around particle

Composition by
Gravimetric Analysis
Ni2+ (aq) + H2DMG Ni(DMG)2 + 2 H+
A

0.8234 g org sample produced

0.1397 g of bis(dimethylglyoximate)
nickel (II) (FW = 288.91 g/mol). Find
the nickel content.
Explain how to create a large,
filterable precipitate.

Combustion Analysis

Find the empirical formula for a 13.72

mg organic sample that produced 6.97
mg of water and 28.44 mg of carbon
dioxide

Gravimetric Overview
Simple
Cheap

Glassware
Reagents
ovens, etc.
Balances

Specific
Timely (1/2 day)
Accurate
Precise (0.1-0.3 %)
Sensitive