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Gravimetric Analysis

gravi metric
(weighing measure)

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
precipitating
reagent
Filter
Dry
Weigh

dissolved
components
sample

precipitating agent

Calculating Amount
of Precipitation Reagent

How many mL of 1% potassium


chloride would be needed to
precipitate all of the silver in a 0.5 g
ore sample that contains 1.5 parts per
thousand silver? Allow for a 15%
excess of the chloride solution.

GravimetricOverview

Measure
tools for gravimetric analysis
filter crucibles, an oven, balance
Calculate
stoichiometry
Report
values
% composition, ppt, ppm, ppb
uncertainty
average
standard deviation, confidence interval

The Precipitation Process


(from solution)

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

Precipitate Formation

von Weimarn: the particles size of pcpt is


inversely proportional to the relative
supersaturation during precipitation process:
Relative Supersaturation = (Q-S)/S

Q = actual solute concentration: degree of


supersaturation
S = equilibrium solute concentration: solubility
The above ratio von Weimarn ratio

Precipitate Formation

Higher degree supersaturation greater


rate of nucleation more crystal with
smaller size large surface area:
increased of impurities adsorption
When nucleation started : initial nucleus
will grow by deposition of other pcpt
particles greater supersaturation
more rapid crystal grow rate increase
chance of imperfections and trapping of
impurities

Controlling Precipitation

Increase S

Increase temperature

Decrease Q
Dilute solution
Well mixed (stirring)

Controlling Precipitation

High Electrolyte
Concentration
to Aid Precipitation
Excess charge on colloid creates
ionic atmosphere around particle

D.C. Harris, Quantitative Chemical

High Electrolyte
Concentration
to Aid Precipitation
Presence another electrolyte will cause
counterions (2nd layer) to be forced into
closer contact with primary layer
promoting coagulation
Washing with water dilute and remove
foreign ions and the counterions occupy
large volume, with more solvent molecule
bteween particle and 1st layer colloidal
state
D.C. Harris, Quantitative Chemical

High Electrolyte
Concentration
to Aid Precipitation

(Christian GD, Analytical Chemistry, 6th

Gravimetric Interferences

Coprecipitated impurities
Surface adsorption
Contaminants bound to the surface
Dry the sample
Mixed crystals
Replacements in the crystal lattice
Reprecipitation
Occlusions/mechanical entrapment
Impurity pockets
Slow digestion/masking agents

Why AgCl?
Reaction

is highly selective - no
interferents

2AgCl ----> 2Ag + Cl2(g)

AgCl

is insoluble in water, i.e., only


slightly soluble in water-losses
negligible

1.4 mg/L at 200C

22 mg/L at 1000C

Why AgCl is a Good


Precipitate?

Small mass of analyte yields large mass


of precipitate-sensitive technique

AgCl precipitates in curds/lumps that


can be easily collected, dried, and
weighed

Precipitate (ppt) is not hygroscopic

Composition by
Gravimetric Analysis
Ni2+ (aq) + H2DMG Ni(DMG)2 + 2 H+
A 0.8234 g ore 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.

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