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Gravimetric Analysis

• Determination of an analyte based on the
mass of a solid
• Simple, but most accurate in chemical analysis
– Extension to this technique is the combustion
analysis
• Involves precipitation reaction at controlled
condition to selectively precipitate species
– Often, we have to remove interfering species
before measurement
Steps in Gravimetric Analysis
Sample dissolution
Precipitation
Digestion
Filtration & washing of ppt
Drying
Weighing
Data calculation
IDEAL:
Insoluble, easily filterable, pure, known
composition
Must have very low solubility
and large particle size
Before doing
experiment,
must know
solubility of
product
Lower total surface
area, minimizing
impurities caused for
co-precipitation
IDEAL:
Insoluble, easily filterable,
pure, known composition


Seldom fulfill requirement


Apply certain technique to
optimize properties of
substance to be measured (ppt)
Steps in Gravimetric Analysis
• Control several parameter
to achieve ideal
precipitate
– Volume of solution
– Type of precipitate agent
– Presence and
concentration of other
species in solution that
may affect precipitation
process
– Temperature of solution
– pH of solution

How
Precipitating Agent
• Types:
– Inorganic : Sulfate, sulfide, chloride
– Organic: 8-hydroxyquinoline, dimethylglyoxime, cupferron,
1-nitroso-2-naphtol
• Some precipitate are gelatinous, and difficult to filter
and weigh
– Usually will be filtered, washed then ignited

Fe (aq) + 3NH
3
(aq) + (x+3)H
2
O  Fe(OH)
3
.xH
2
O (s) + 3NH
4+
(aq)


Fe(OH)
3
.xH
2
O (s) + 3NH
4+
(aq) → Fe
2
O
3
(s) + (2x+3)H
2
O



Precipitating Agent
• Organic precipitate  usually been used to
achieved high MW ppt
• Advantages:
– Ppt is less soluble in H
2
O
– Less impurities due to co-precipitate
– Higher MW, less error in wt.
– Few organic ppt agent act as chelating agent to
form colored complex, for easy detection by
colorimetry
Dimethylglyoxime (DMG)
• Selective
• Reacts with Ni
2+
 red DMG-Ni complex in
slightly alkaline solution
(MW 58.69) DMG (MW 116.12)
Bis(dimethylglyoximate)nickel(II)
8-hydroxyquinoline (Oxine)
• Common complexing
agent for more than 13
metal ions
• Forms:
– 2:1 complex with
divalent metal ions
– 3:1 complex with metal
ions
• A weak acid
– Different cathion,
different complex
stability
– Depends of pH of
solution
Al(C
9
H
6
NO)
3
: pH 4
Mg(C
9
H
6
NO)
2
: higher pH

+ Al
3+


Al
O
3

+ 2H
+
Tris(8-hydroxyquinolate)Al(III)
(FW 459.441)
(MW 26.98)
3
Mixture can
be separated
But at higher pH (≈ pH 9), may
result in co-ppt of Mg(OH)
2
Precipitation
• We want large size ppt  Easy to filter
Supersaturation Nucleation
Particle/
crystal
growth
Aggregation
Colloid
Fine
crystal
Course
crystal
R
nucleation
>
R
particle growth
R
nucleation
<
R
particle growth

More solute than
should be present
at equilibrium


Add ppt agent
into solution
Molecules
combine
randomly


Small aggregate
(nucleus)
More ions are
added to
nucleus


Colloids/
colloidal particle
(1-1000 nm)
Particle
colloids

Larger
particle How?
Effect of Supersaturation
• Supersaturation = Q – S

High (Q – S): High supersaturation
Many nuclei, with
small particle
Von Weimann principle :
ation Supersatur
1
size Particle α
Relative
supersaturation
S
S - Q

Q↑, S↓ = ↑ supersaturation  fine particle
Q↓, S↑ = ↓ supersaturation  course particle
Nucleation Particle
growth
R
S
S - Q
Example – Precipitation of AgCl
• Analysis of Cl
-
ion, using AgNO
3
ppt agent, in
presence of 0.1 M HNO
3
AgCl (p) ↔ Ag (aq)
+
+ Cl
-
(aq)





– Particle grow in solution
with excess H
+
, Ag
+
& NO
3
-
H
+

Ag
+

NO
3
-

Nucleus
Example – Precipitation of AgCl
Colloidal particle:
net +ve charge
(extra Ag
+
on exposed Cl
-
)
Ionic atmosphere:
net –ve charge
Attract anions
(eg., NO
3
-
),
repel cations
(e.g.: H
+
)
ELECTRIC DOUBLE LAYER
How to
coalesce?
Heat solution
↑[electrolyte]
↓ vol. of ionic
atmosphere
Closer
particles
*Most gravimetric pptn
been carried out in
presence of electrolyte
↑ E
K
of
particles
To coalesce, colloidal particle must
collide each other with enough E
K
to
overcome repulsion
Achieving Low Supersaturation
• Must control condition to minimize
supersaturation
– Crystallization at ↑ T: ensure ↓ supersaturation
– + ppt agent slowly with vigorous mixing to
avoid local, ↑ly supersaturated region
– Keep vol of solution large to keep *analyte+ ↓
– Homogenous pptn
• Pptn agent is not added directly, but generated
slowly by chemical rxn on the solution
• Slow enough rxn, avoiding ↑ supersaturation
Throughout
experiment
– Do digestion after pptn
Achieving Low Supersaturation
• Must control condition to minimize
supersaturation
– Crystallization at ↑ T: ensure ↓ supersaturation
– + ppt agent slowly with vigorous mixing to
avoid local, ↑ly supersaturated region
– Keep vol of solution large to keep *analyte+ ↓
– Homogenous pptn
• Pptn agent is not added directly, but generated
slowly by chemical rxn on the solution
• Slow enough rxn, avoiding ↑ supersaturation
Throughout
experiment
Example:
Slow generation of OH
-
(ppt agent) from urea
decomposition in H
2
O (1 – 2 hrs), for ppt of Al(III) and Fe(II)


 


     2OH 2NH CO O 3H CO N H
4 2
Δ
2 2 2
Common reagents for homogenous pptn
Reagent
Ppt
agent
Rxn
Eg. of elements
pptd
Urea OH
-
(H
2
N)
2
CO + 3H
2
O  2NH
4
+
+ 2OH
-
Al, Ga, Th, BI,
Fe, Sn
Potassium cyanate OH
-
HOCN + 2H
2
O  NH
4
+
+ CO
2
+ OH
-

Cr, Fe
Thioacetamide S
2-
CH
3
CNH
2
+ H
2
O  CH
3
CNH
2
+ H
2
S
Sb, Mo, Cu, Cd
Sulfamic acid SO
4
2-
H
3
N
+
SO
3
-
+ H
2
O  NH
4
+
+ SO
4
2-
+ H
+
Ba, Ca, Sr, Pb
Dimethyl oxalate C
2
O
4
2-
CH
3
OC-COCH
3
+ H
2
O 2CH
3
OH + H
+
+ C
2
O
4
2-
Ca, Mg, Zn
Chromic ion plus
bromate
CrO
4
2-
2Cr
3+
+ BrO
3
-
+ 5H
2
O  2CrO
4
2-
+ Br
-
+ 10H
+
Pb
S O
O O
Impurities of Particles
• Ppt obtained are often impure
– Foreign substance ppt along analyte
• Types:
– Adsorbed impurities
– Absorbed impurities
Co-precipitation
• Process where impurity is precipitated
along with desired ppt, even though
solubility of impurity has not be
exceeded
Serious in colloidal ppt
Eg: BaSO
4
, Al(OH)
3
, Fe(OH)
3
(large surface area)
Major contribution
to error
Impurities of Particles
BaCl
2
FeCl
3
H
2
SO
4
Supposedly
BaSO
4
being
pptd, Fe(SO
4
)
3

remain in
solution
Contaminated with
brown Fe
2
O
3

(decomposition of
co-ppt Fe(SO
4
)
3

during heating)
Filter, wash, ignite
Adsorbed Impurities
• Attached to surface of crystal
• A reversible process, can reach equilibrium



• Adsorption: exothermic process
– ↑T, ↓ adsorbed impurities
Govern by:
• Surface A of ads
• T
• [ion]
• Characteristic of
adsorbed ions
Amount of
adsorbed
substance
α
Surface A of
adsorbent
Significant in
colloidal/
gelatinous ppt
Adsorbed Impurities
• 2 types: Primary adsorption
• Ppt adsorb its own ion
or isomorphous ion

Forming monolayer on particle
surface; net –ve/+ve charge



Forms diffuse layer
(secondary adsorption)
↑ with ↑ing charge on ion adsorbed ions

Ppt
+
-
-
-
-
-
-
-
-
+
+
+
+
+
+
+
+
+
+
+
Secondary
(net +ve)
Primary
(net -ve)
Attracts
counter ion
Absorbed Impurities
• Within the crystal

Inclusion
– Occupy sites in crystal
lattice by
substituting/being in
between
– Difficult to rectify
• Digestion only helps to a
small extent
– Can’t be remove by
washing, but may be ↓ by
recrystallization
Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

SO
4
2-
Ba
2+
SO
4
2-
Pb
2+

Pb
2+
SO
4
2-
Ba
2+
SO
4
2-

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

SO
4
2-
Ba
2+
SO
4
2-
Ba
2+

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

Inclusion
Occlusion
K
+
K
+
Likely when
impurity ion
has similar
size and
charge
K+ :
different in
ionic charge
Absorbed Impurities
Occlusion
– Pockets of impurities
trapped inside a rapidly
growing crystal
– 2 form
New layer form on
crystal surface
Impurities adsorbed
on the layer & pptd
Ppt grow, impurities
will be displaced
(but not completely)
Aggregate
occlusion
Crystalline
occlusion
―Caused by
internal
adsorption
―Affected by
mixing sequence
Absorbed Impurities
Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

SO
4
2-
Ba
2+
SO
4
2-
Ba
2+
SO
4
2-
Ba
2+

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

SO
4
2-
Ba
2+

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

SO
4
2-
Ba
2+
SO
4
2-
Ba
2+
SO
4
2-
Ba
2+

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

Ba
2+
SO
4
2-
Ba
2+
SO
4
2-

Occlusion
– 2 types
Aggregate
occlusion
Crystalline
occlusion
Ba
2+

Ba
2+

Cl
-

Cl
-

H
2
O
H
2
O
H
2
O
BaSO
4
BaCl
2
Ba
2+
Ba
2+
H
2
SO
4
Mixture of H
2
SO
4
and BaCl
2
BaSO
4
H
2
SO
4
SO
4
-
SO
4
-
BaCl
2
Small-sized
colloids/crystallites
aggregate with each
other
Forming Larger
particle
Impurities in solution can
be trapped in voids
between crystallites
Minimizing Impurities
• Numbers of techniques can
be used
• Most impurities can be
removed by washing or
redissolving ppt followed by
reprecipitation
• Impurities can be minimized
by proper pptn techniques
and masking
Digestion
• Practiced in most
gravimetric analysis
• Ppt is allowed to keep
contact with mother
solution, usually with
heating
• Promotes slow
recrystallization of ppt
– ↑ particle size, ↓ impurities
Washing
• Washing ppt on filter tends
to remove remaining liquid
which contain excess solute
• Some ppt can be wash with
H
2
O
• But mostly with solution
containing volatile/easily
decompose electrolyte to
maintain coherence
– Electrolytes replaces initial
adsorbed electrolyte impurity
– Surface charge of particle is
neutralized by ionic solvent

Washing with H
2
O
• Disturb counter–primary
ion interaction
• Charged solid will repel
each other & breaking up
(“peptization”)
– Eg.: AgCl peptize with H
2
O,
thus, wash with dilute HNO
3
• Commonly used:
– HNO
3
, HCl, NH
4
NO
3
, NH
4
Cl &
(NH
4
)
2
CO
3
Masking
• Prevent impurities to react wit ppt agent
Ca
2+
+ 2RH  CaR
2
(s) + 2H
+

Mn
2+
+ 6CN
-
 Mn(CN)
6
4-
Analyte
Impurity
Precipitant
Masking agent
Ppt
Stays in solution
Reagent Analyte Masking agent Masked ion
N-p-chlorophenyl-
cinnamohydroxamic
acid (NCPCH acid)
Be2+, Mg2+,
Ca2+, Ba2+
KCN Ag
+
, Mn
2+
, Zn
2+
,
Cd
2+,
Hg
2+
, Fe
2+

and Ga
3+

(Same as above) (Same as above) Mixture of citrate
and oxalate
Pb
2+
, Pd
2+
, Sb
2+
,
Sn
2+
, Bi
2+
, Zr
4+
,
Ti
4+
, V
5+
and Mo
6+
Drying
• In gravimetric analysis, final
product must have known,
stable composition
– Some ppt are dried in oven at
110 – 120°C to for several hrs
to drive off excess solvent
– Alternative: Microwave oven
for shorter period of time
– Hygroscopic substance is
difficult to weigh accurately
• Absorbs moisture from
surrounding
• Some other ppt contain
variable quantity of H
2
O and
must be dried under
conditions that give
stoichiometry of H
2
O
– Drying often carried out until
constant wt.
– Strong heating (aka ignition)
used to change chemical form
of certain ppt

Fe(HCO
2
)
3
.nH
2
O Fe
2
O
3
Mg(NH
4
)PO
4
.6H
2
O Mg
2
P
2
O
7
    
hr 1 C, 850
o
 