Gravimetric Analysis

1
Gravimetric Analysis- What is It?
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
Gravimetric Analysis- What is It?
Reaction:
aA + rR -----> A
a
R
r ppt
where:
a is # of moles of analyte A
r is # of moles of reagent R
A
a
R
r
is a pure, insoluble precipitate
which we can dry and weigh or ignite
to convert to something we can weigh
ppt=precipitate
T.W.Richards
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. As little as
possible must be taken for granted.
6
How to Perform a Successful
Gravimetric Analysis
What steps are needed?
1. Sampled dried, triplicate portions weighed
2. Preparation of the solution
3. Precipitation
4. Digestion
5. Filtration
6. Washing
7. Drying or igniting
8. Weighing
9. Calculation
7
Gravimetric Analysis
Gravimetric Analysis one of the most accurate
and precise methods of macro-quantitative
analysis.
Analyte selectively converted to an insoluble
form.
Measurement of mass of material
Correlate with chemical composition
Why?
Simple
Often required for high precision

8
Determination of mass


Direct
By difference
NaHCO
3
+ H
2
SO
4
CO
2
+ H
2
O +NaHSO
3
Determination of NaHCO
3

10
Desirable properties of
analytical precipitates

Readily filtered and purified
Low solubility, preventing losses during
filtration and washing
Stable final form (unreactive)
Known composition after drying or ignition

Suction Filtration
Filter flask
Buchner funnel
Filter paper
Glass frit
Filter adapter
Heavy-walled rubber
tubing
Water aspirator
Suction Filtration
Mother liquor
13
Kinds of Precipitating reagents:
Selective
Ag
+
+ Halides (X
-
) AgX
(s)
Ag
+
+ CNS
-
AgCNS
(s)
Specific
Dimethylglyoxime (DMG)
2 DMG + Ni
2+
Ni(DMG)
2(s)
+ 2 H
+

14
Mechanism of Precipitation
15
Fig. 10.2. Representation of silver chloride colloidal particle
and adsorptive layers when Cl
-
is in excess.
Cl
-
adsorbs on the particles when in excess (primary layer).
A counter layer of cations forms. The
neutral double layer causes the colloidal particles to coagulate.
Washing with water will dilute the counter layer and the primary layer charge causes the
particles to revert to the colloidal state (peptization).
So we wash with an electrolyte that can be volatilized on heating (HNO
3
).
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

16
Filterability of Precipitates

Colloidal suspensions
10
-7
to 10
-4
cm diameter
Normally remain suspended
Very difficult to filter
Crystalline precipitates
> tenths of mm diameter
Normally settle out spontaneously
Readily filterable
17
R.S.S = (Q-S)/S

Precipitate formation affected by:
Solubility of Precipitate
Temperature
Concentration of reagens
Rate of mixing
-Relative Super Saturation(R.S.S)
R.S.S = (Q-S)/S
Q = Instantaneous Concentrations of the mixed reagents
S = Equilibrium Solubility of Precipitate
Smaller R.S.S leads to crystalline precipitates.
Q S
18
Conditions for Analytical
Precipitation
Precipitation from hot solution
The molar solubility (S) of precipitates increases with
an increase in temperature
An increase in S decreases the supersaturation and
increases the size of the particle.
Precipitation from dilute solution
This keeps the molar concentration of the mixed
reagents low. Slow addition of precipitating reagent
and thorough stirring keeps Q low. (Uniform stirring
prevents high local concentrations of the precipitating
agent.)
19
Conditions for Analytical
Precipitation
Precipitation at a pH near the acidic end of the
pH range in which the precipitate is quantitative.
Many precipitates are more soluble at the lower (more
acidic) pH values and so the rate of precipitation is
slower.
Digestion of the precipitate.
The digestion period can lead to improvements in the
organization of atoms within the crystalline nuclei, such
as expulsion of foreign atoms (or other impurities).
20
Important Factors for Gravimetric Analysis
Nucleation (RSS)
n
Individual ions/atoms/molecules coalesce to
form nuclei
Particle Growth (RSS)n
Condensation of ions/atoms/molecules with
existing nuclei forming larger particles which
settle out
Competition
21
Important Factors for Gravimetric
Analysis
Colloidal Suspension
Colloidal particles remain suspended due to:
small size
adsorbed ions giving a net + or charge
(Brownian motion)

22

Important Factors for Gravimetric Analysis
Coagulation, agglomeration
Suspended colloidal particles coalesce to form larger
filterable particles by:
Heating
stirring
adding inert electrolyte

23
24
25
AgCl (s) AgCl (colloid)
Peptization

Re-dissolution of coagulated colloids by :
washing and removing inert electrolyte
26
Digestion
Heating the precipitate within the mother liquor (or solution
from which it precipitated) for a certain period of time to
encourage densification of nuclei.
During digestion, small particles dissolve and larger
ones grow. This process helps produce larger crystals
that are more easily filtered from solution
DT
27
Fig. 10.1. Ostwald ripening.
During digestion at elevated temperature:
Small particles tend to dissolve and reprecipitate on larger ones.
Individual particles agglomerate.
Adsorbed impurities tend to go into solution.
Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

28
Ideal Analytical Precipitation
In an ideal world, an analytical precipitate for gravimetric
analysis should consist of perfect crystals large enough to
be easily washed and filtered.
The perfect crystal would be free from impurities and
be large enough so that it presented a minimum surface
area onto which foreign ions could be adsorbed.
The precipitate should also be "insoluble" (i.e., low
solubility such that loses from dissolution would be
minimal).
29
Increasing Purity
Re-precipitation
a procedure including washing away the mother liquor,
redisolving the precipitate, and precipitating the product
again
Structure of a Colloid
Why do two colloid particles resist
aggregating to form a crystal?
If two colloid particles, each with a negative
charge, come close to one another, they will
repel!
So colloid particles are stable and resist
crystal formation.
Coagulating a Colloid
What can be done to overcome this colloid
stability and force crystals to form?
High heat, stirring, only a slight excess of
the excess reagent, and the addition of an
electrolyte can force a colloid to coagulate
into crystals.
Coagulating a Colloid
High heat, initially with stirring, is thought
to lower the thickness of the double layer,
thus making it easier for two colloid
particles to collide and coagulate.
The higher kinetic energy will also help
them gain enough energy to overcome
the repulsion.
Coagulating a Colloid
If too much of the excess reagent is added,
then the double layer increases in volume as
more of the excess solute ions will be
adsorbed to the surface, which in turn
requires a larger counter-ion layer.
Coagulating a Colloid

So it is important to make sure that there is only a
slight excess of the excess reagent.
Thus the diameter of the double layer will be
minimized, enabling neighboring colloids to
coagulate.
Coagulating a Colloid
On the other hand, the addition of a suitable
electrolyte like nitric acid or hydrochloric acid
may also lower the diameter of the double layer.
Now the high concentration of the appropriate ion
will make it easier to form the counter-ion layer
and its thickness will be reduced.
Again, two neighboring colloids can get closer
together, making it easier to coagulate.
Digesting
Once a colloid starts to coagulate, it is best
to digest the solution.
Digestion is when the heated solution with
the coagulating crystals sits undisturbed for
an hour or more.
Digesting
Typically, the colloidal suspension is stirred with
heating until crystals start to coagulate.
Then stirring is stopped, and the solution is heated
to almost boiling for at least 10 minutes.
Finally, the solution is allowed to cool slowly and
sit undisturbed for several hours.
Digestion results in larger, purer crystals which
are easier to filter.
Filtration
Once the crystals have formed and digested,
they need to be filtered.
The washing step can be a problem, as
peptization of the coagulated colloid may
occur.
This means that the coagulated colloid
reverts to a smaller colloidal particle.
Filtration
Washing with pure water often causes this
problem as this lowers the concentration of
counter-ions, which then causes the double
layer to increase in volume, and the
coagulated solid may break back into
smaller colloids.
These colloids will then go right through the
filter, and the filtrate may look cloudy.
Filtration
Typically, the wash solvent is a dilute
solution of the electrolyte.
This keeps the double layer intact,
minimizing peptization.
This electrolyte will then volatilize during
the drying step.
The filtered and washed crystals are then
dried to constant mass.
Coprecipitation of Impurities
During the precipitation process, other soluble
compounds may also be removed from the
solution phase.
These other compounds are carried out of solution
by the desired crystals.
They are impurities and they are said to have
coprecipitated.
These are NOT other insoluble compounds, but by
several mechanisms, have been carried out of
solution.
Coprecipitation of Impurities
Coprecipitation occurs in several ways:
adsorption onto the surface of the crystals,
inclusions (absorption into crystal)
occlusions (absorption)
Inclusions occur when ions of the impurity
occupy lattice sites in the crystal, while
occlusions are just particles which are
physically trapped inside the crystal
Reprecipitation
If coprecipitation occurs or is known to be a
common occurrence with this solute, then
reprecipitation of the solute should be
conducted.
In reprecipitation, the filtered precipitate
containing impurities is redissolved and
then the crystals are reprecipitated.
Reprecipitation
This technique effectively lowers the
concentration of impurities, so the second
precipitation will contain fewer
impurities.
This is a common technique for iron and
aluminum hydroxides which coprecipitate
other more soluble hydroxides.
45
Co-precipitation

Normally soluble compounds carried down
with insoluble precipitate.


1)Equilibrium process
2)Kinetic of growth process
46
Co-precipitation
1)Equilibrium process

surface adsorption, Is improved by:
Digestion, washing, re-precipitationi
Co-precipitation

mixed crystals
A type of coprecipitation in which the
impurities occupy the crystal lattice
sites
mixed crystal
(MgKPO4 & Mg NH4PO4)
Is improved by:
Primary separation
48
Co-precipitation

2)Kinetic of growth process
occlusion, Rapid growth (Foreign ions)

Slow rate, digestion & reprecipitation

49
Co-precipitation

Entrapment, (portion of solution)
Is improved by:




Slow rate, digestion & reprecipitation

Gathering Agents
Occasionally, reprecipitation is intentionally used
to gather a trace component that coprecipitates.
When the precipitate is redissolved in a very small
amount of solvent, the trace component has been
effectively concentrated.
In this case, the precipitate used to gather the trace
component is called the gathering agent.
Masking Agents
Masking agents can also be used to prevent
coprecipitation.
The masking agents react with the
impurities to from highly soluble
complexes to keep them in solution.
Homogeneous Precipitation
In homogeneous precipitation, the
precipitate is formed through a second
chemical reaction.
First, a reagent is treated in a manner so that
it forms what is called a precipitating agent
or reagent.
The precipitating reagent then reacts with
the solute ion to form the desired solid
precipitate.
Homogeneous Precipitation
As the precipitating reagent is generated in
the solution gradually, this limits the
relative supersaturation of the precipitate.
So crystals are more likely to form, be
larger, and be more pure.
This is relatively common for the
precipitation of hydroxide salts where urea
is used to generate the precipitating agent
hydroxide.
Drying a Precipitate
Drying a precipitate seems easy.
Many compounds can be easily dried at around
110C to remove any water which is adsorbed.
Other compounds need much higher heat to
remove water.
The temperature must be carefully decided as
many compounds will decompose if the heat is too
high.
Common Desiccants
Mechanism of Action
Hydration ANHYDRONE
(Magnesium Perchlorate
anhydrous), CaCl2,
MgO, MgSO4, K2CO3,
KOH, Drierite, Na2SO4
(anhydrous), H2SO4,
ZnCl2
Absorption and/ or
Adsorption
BaO, CaSO4, Molecular
Sieve, H3PO4, NaOH
Pellets
Chemisorption CaO, P2O5

Silica gel goes from blue to
pink as it absorbs moisture
Can be regenerated in oven
Anhydrous sodium sulfate
gets clumpy as it absorbs
water
More Information about desiccants including common
interferents and regeneration temperature can be found
at:
http://www.jtbaker.com/techlib/documents/3045.html
Igniting a Precipitate
Yet other precipitates have a variable composition
and must be further treated to form a compound of
uniform composition.
One common way to treat variable composition
compounds is through ignition: high heating.
This is common with iron analysis. Variable
composition ferric bicarbonate hydrates are
ignited at around 850C to produce anhydrous
ferric oxide.
59
Alternative Gravimetry Technique
Homogeneous Precipitation
What?
Precipitating agent generated slowly by chemical reaction in
analyte solution
Why?
Precipitant appears gradually throughout
Keeps relative supersaturation low
Larger, less-contaminated particles
How?
(OH
-
) by urea decomposition
(NH
2
)
2
CO 2 OH
-
+ CO
2
+ 2 NH
4
+

(S
=
) by thioacetamide decomposition
CH
3
CSNH
2
H
2
S + CH
3
CONH
2
(DMG) from biacetyl + hydroxylamine
CH
3
C(=0)-C(=0)CH
3
+ 2 H
2
NOH DMG + 2 H
2
O



Fig 12-5, p.324
60
Species
analyzed
Precipitated form Form weighed Some interfering
species
K
+
KB(C
6
H
5
)
4
NH
4
+
, Ag
+
, Hg
2+
, Tl
+
, Rb
+
,
Cs
+
Mg
2+
Mg(NH
4
)PO
4
.6H
2
O Mg
2
P
2
O
7
Many metals except Na
+

and K
+
Ca
2+
CaC
2
O
4
.H
2
O CaCO
3
or CaO Many metals except Mg
2+
,
Na
+
, or K
+
Ba
2+
BaSO
4
BaSO
4
Na
+
, K
+
, Li
+
, Ca2+, Al3+,
Cr
3+
, Fe
3+
, Sr
2+
, Pb
2+
,
NO
3
-
Ti
4+
TiO(5,7-dibromo-8-
hydroxyquinoline)
2
same Fe
3+
, Zr
4+
, Cu
2+
, C
2
O
4
2-
,
citrate, HF
VO
4
3-
Hg
3
VO
4
V
2
O
5
Cl
-
, Br
-
, I
-
, SO
4
2-
, CrO
4
2-
,
AsO
4
3-
, PO
4
3-
Cr
3+
PbCrO
4
Ag
+
, NH
4
+
Mn
2+
Mn(NH
4
)PO
4
.H
2
O Mn
2
P
2
O
7
Many metals
Fe
3+
Fe(HCO
2
)
3
Fe
2
O
3
Many metals
Ni
2+
Ni(dimethylglyoximate)
2
same Pd
2+
, Pt
2+
, Bi
3+
, Au
3+
63
64
Organic precipitating agents are chelating agents.
They form insoluble metal chelates.

Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley)

Table 12-2, p.330
Table 12-3, p.330
67
68
69
8-Hydroxyquinoline
Gravimetric Analysis
Mg
2+
+ 2
N
O H
+ 2H
+
N
O
M g
O
N
Selectivity through pH control
8-Hydroxyquinoline Examples
Gravimetric Analysis
Metal pH
Initial Ppt.
pH
Complete
Ppt
Metal pH
Initial Ppt.
pH
Complete
Ppt
Aluminium 2.9 4.7 9.8 Manganese 4.3 5.9 9.5
Bismuth 3.7 5.2 9.4 Molybdenum 2.0 3.6 7.3
Cadmium 4.5 5.5 13.2 Nickel 3.5 4.6 10.0
Calcium 6.8 9.2 12.7 Thorium 3.9 4.4 8.8
Cobalt 3.6 4.9 11.6 Titanium 3.6 4.8 8.6
Copper 3.0 >3.3 Tungsten 3.5 5.0 5.7
Iron(III) 2.5 4.1 11.2 Uranium 3.7 4.9 9.3
Lead 4.8 8.4 12.3 Vanadium 1.4 2.7 6.1
Magnesium 7.0 >8.7 Zinc 3.3 >4.4
Dimethylglyoxine
Gravimetric Analysis
Weakly alkaline conditions

Nickel salt bright red
Ni
2+
+ 2
C H
3
C C C H
3
N N
H O O H
+
C H
3
C C C H
3
N N
N i
O O
O O N N
C H
3
C C C H
3
H
H 2H
+

73
75
Conversion

Removal of volatile reagents & solvent
Extended heating at 110 to 115
O
C
Thermal Conversion to Measurable Form
Chemical conversion to known stable form
CaC
2
O
4(s)
CaO
(s)
+ CO
(g)
+ CO
2(g)

Volatilization & trapping of component
NaHCO
3(aq)
+ H
2
SO
4(aq)
CO
2(g)
+ H
2
O + NaHSO
4(aq)
76
Combustion Analysis
Combustion analysis is still used to determine the
amount of C, H, N, O, S, and halogens in an
unknown sample.
In the classic freshman combustion problem, a
hydrocarbon is combusted in excess oxygen gas to
produce water vapor and carbon dioxide gas.
The water and carbon dioxide are trapped and the
mass of these products is obtained.
Then calculations begin.
Combustion Analysis
Today, elemental combustion analyzers
measure C, N, H, and S at the same time.
Oxygen analysis is done through pyrolysis
with no oxygen gas and halogen analysis
occurs through an automated titration.
Other Gravimetric Techniques
83
Combustion Analysis, or Elemental Analysis
(g) SO (g) SO (g) N O(g) H (g) CO S N, H, C,
3 2 2 2 2
C 1050


Determines the C, H,
N, and S content in a
single operation by
using GC and thermal
conductivity
measurements
Other Gravimetric Techniques
84
Combustion Analysis, or Elemental Analysis cont.
Other Gravimetric Techniques
85
Thermal Gravimetric Analysis (TGA)
Precisely monitoring
weight loss of a sample
in a given atmosphere
as a function of
temperature and/or time

Atmospheres: N
2
, O
2
, air, or He
Temperature: ambient to 1000 C
Records the first derivative of the
mass loss
Other Gravimetric Techniques
86
TGA cont.
Evaluate the thermal decomposition and stability of
materials
Polymers, resins, rubbers, explosives

Information on bulk composition of compounds
Thermal oxidation, heat resistance
Residual water or solvents
Compositional analysis
Ash content in a sample
Quantity of inorganic filler in a polymer
Other Gravimetric Techniques
87
The percent weight loss of a test sample is recorded while
the sample is being heated at a uniform rate in an appropriate
environment.
The loss in weight over specific temperature ranges provides
an indication of the composition of the sample, including
volatiles and inert filler, as well as indications of thermal
stability.
The gas environment is pre-selected for either a thermal
decomposition (inert He or N
2
gas), an oxidative
decomposition (air or O
2
), or a combination therein.

TGA cont.
TGA Instrumentation
88
http://radchem.nevada.edu/chem455/lecture_22__thermal_methods.htm
1. A sample (0.1 to 15 mg) is
placed into a tared TGA
sample pan, which is
attached to a sensitive
microbalance.
2. The sample holder
(connected to the balance) is
subsequently placed into a
high temperature furnace.
3. Balance assembly measures
the initial sample weight at
room temperature and
continuously monitors
changes in sample weight
(losses or gains) as heat is
applied to the sample (up to
1500 C).
TGA tests may be run in a
heating mode at some
controlled heating rate, or
isothermally. Typical weight
loss profiles are analyzed for
the amount or percent of
weight loss at any given
temperature, the amount or
percent of noncombusted
residue at some final
temperature, and the
temperatures of various sample
degradation processes.
89
TGA cont.
90
H
2
O, C
7
H
3
O
6
,
C
6
H
4
, CO
2
are
consecutively lost.
TGA cont.
91
Gravimetric Calculations
Gravimetric Factor (GF):
A2B
(s)

GF = g A/g B
GF = (FW A /FW B)x(a moles A/b moles B)
BaCl
2
+2AgNO
3
Ba(NO
3
)
2
+ 2AgCl
(s)



1 ) (
2 ) (
2

BaCl FW
AgCl FW
GF
The Gravimetric Factor
G.F. = a FW[analyte]
b FW[precipitate]

Analyte ppt G.F.
CaO CaCO
3

FeS BaSO
4

UO
2
(NO
3
)
2
.
6H
2
O U
3
O
8

Cr
2
O
3
Ag
2
CrO
4

Gravimetric Factor
Analyte ppt G.F.
CaO CaCO
3
CaO/CaCO
3

FeS BaSO
4
FeS/BaSO
4

UO
2
(NO
3
)
2

U
3
O
8
3UO
2
(NO
3
)
2
/U
3
O
8

Cr
2
O
3
Ag
2
CrO
4
Cr
2
O
3
/2Ag
2
CrO
4


Naming is critically important (next class)

94
Gravimetric Errors
Co-precipitation: (with AgCl)
Co-precipitant Error Rationale
NaF Positive All NaF is excess
NaCl Negative Fwt Na<Ag
AgI Positive All AgI is excess
PbCl
2
(fwt 278.1) Negative Gravimetric
Factors decreases
95
Calculating Results from Gravimetric Data
The calcium in a 200.0 ml sample of a
natural water was determined by
precipitating the cation as CaC
2
O
4
. The
precipitate was filtered, washed, and ignited
in a crucible with an empty mass of 26.6002
g. The mass of the crucible plus CaO (fwt
56.077 g/mol) was 26.7134 g. Calculate the
concentration of Ca (fwt 40.078 g/mol) in
the water in units of grams per 100 mL.
96
Calculating Results from Gravimetric Data
An iron ore was analyzed by dissolving a
1.1324 g sample in concentrated HCl. The
resulting solution was diluted with water,
and the iron(III) was precipitated as the
hydrous oxide Fe
2
O
3
.
xH
2
O by addition of
NH
3
. After filtration and washing, the
residue was ignited at high temperature to
give 0.5394 g pure Fe
2
O
3
(fwt 159.69
g/mol). Calculate (a) the % Fe (fwt 55.847
g/mol) and (b) % Fe
3
O
4
(fwt 231.54 g/mol)
in the sample.
97
Calculating Results from Gravimetric Data
A 0.2356 g sample containing only NaCl
(fwt 58.44 g/mol) and BaCl
2
(fwt 208.23
g/mol) yielded 0.4637 g of dried AgCl (fwt
143.32 g/mol). Calculate the percent of
each halogen compound in the sample.
Vial containing the unknown
Two 400 mL beakers and two stir rods.
60 mL of 0.55 M CaCl
2
Crucible tongs
Beaker tongs
Desicooler
Crucibles
Drying agent
Obtain two crucibles from the oven, put the lid on and let them
cool on the bench top for 20 min. Then weigh them accurately on
the analytical balance.
Use crucible tongs to transfer
crucible to analytical balance.
Record the mass in your notebook.
Accurately determine the mass of the vial, contents
and lid. Record this mass and unknown #.
Tap out about half of
the unknown into one
of the 400 mL beakers.
(Label this beaker)
Reweigh accurately the vial with
the lid and record this mass.
Tap the remaining unknown
into the other 400 mL
beaker (label it).
Reweigh accurately the vial.
Pour about 20 mL of distilled water into each of the 400 mL
beakers. Swirl (gently) to dissolve the unknown sample, and warm
the beakers a little if youre having trouble dissolving the sample.
Once the unknown
samples have
dissolved, add about
80 mL more distilled
water to each beaker
and cover each
beaker with a watch
glass and warm them
to steaming.
Steaming
Once solutions have
started steaming, reduce
the heat to medium- low
and add 30 mL of 0.55 M
CaCl
2
to each solution.
Stir each solution with its
own stir rod for a few
seconds, then leave the
stir rod in the solutions
and allow them to heat
for another 30 min.
When about 30
minutes is up and the
precipitated has
settled, add one or
two drops of CaCl
2
to
the supernatant liquid.
If no additional
precipitate forms take
the beakers and put
them in an ice water
bath to cool.
Ice water bath.
Aspirator
Suction cone
Utility clamp
Vacuum filter flask
Stand
Black vacuum (rubber) tubing
Crucible
Filter the solution
through one of the
pre-weighed
crucibles.
Rinse and filter the
precipitate in the
beaker several times
with a small quantity of
cold distilled water.
Place the crucibles in the desicooler.
And in the oven overnight to dry.
The next day come
and weigh the
crucibles. Record
their masses.
The figure on the
right shows the
reaction of
Ba(NO
3
)
2
with
K
2
CrO
4
forming
the yellow
BaCrO
4

precipitate.
The BaCrO
4

precipitate is
being filtered in
the figure on the
right. It can then
be dried and
weighed.