C1013- General and

Inorganic Chemistry

Unit 2: Thermodynamics in
Titrimetry and Gravimetry

OUTLINE
Some basics of inorganic analytical
chemistry
Titrimetry
Precipitation reactions
Acid base reactions
Redox reactions

Basics of Inorganic Analytical

Chemistry
The main techniques employed in
quantitative inorganic analysis are
based upon
The quantitative performance of
suitable chemical reactions and either
measuring the amount of reagent
needed to complete the reaction or
ascertaining the amount of reaction
product obtained.
Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry
Appropriate electrical measurements
(e.g. potentiometry)
The measurement of certain optical
properties (e.g. absorption spectra)
In some case a combination of above
three (e.g. amperometric titration)

Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry
The quantitative execution of
chemical reactions is the basis of the
TRADITIONAL or CLASSICAL methods
of chemical analysis.
Gravimetry
Titrimetry
Volumetry
Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry
In gravimetric analysis the substance being
determined is converted into an insoluble
precipitate which is collected and weighed
OR
In the special case of electrogravimetry,
electrolysis is carried out and the material
deposited on one of the electrodes is weighed.

Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry
In titrimetric /volumetric analysis, the substance
to be determined is allowed to react with an
appropriate reagent added as a standard
solution and the volume of standard solution
needed for complete reaction is determined.

Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry
Common types of titrimetry are,
a) Neutralisation reactions
b) Complex forming reactions
c) Precipitation reactions
d) Redox reactions

Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry
Volumerty is concerned with
measuring the volume of gas evolved
or absorbed in a chemical reaction.

Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry

Electrical methods of analysis involve the measurement of

current, voltage or resistance in relation to the concentration
of a certain species in solution. Some of them are
Voltametry
Coulometry
Potentiometry
Conductimetry

Vogel's Text book of Quantitative Inorganic Analysis

Basics of Analytical
Chemistry

Optical methods of analysis are dependent

on
The absorption of radiant energy and the measurement
of the amount of energy absorbed by the sample
The emission of radiant energy and measurement of the
amount of energy of a particular wavelength emitted.

Vogel's Text book of Quantitative Inorganic Analysis

Some keywords in Titrimetry

Standard solution Reagent of
exactly known concentration.
Titration Is a process in which a
standard reagent is added to a
solution of an analyte until the
reaction between the analyte and the
reagent is judge to be complete

Some keywords in Titrimetry

Back Titration A process where
the excess of a standard solution
used to consume an analyte is
determined by titration with a second
standard solution
Especially used when
the reaction rates are slow between analyte
and the reagent
When standard solution lacks stability

Some keywords in Titrimetry

Equivalence point The point in a
titration when the amount of added
standard reagent is exactly
equivalent to the amount of analyte.
End Point The point in a titration
when a physical change occurs that
is associated with the condition of
chemical equivalence.

Some keywords in Titrimetry

Primary Standards Ultrapure
compund that serves as the
reference material for a titrimetric
analysis.

High Purity
Atmospheric stability
Absence of hydrate water
Modest cost
Solubility in the titration medium
Lager molar mass to minimise errors with
weighing

Some keywords in Titrimetry

Secondary Standards A
compound whose purity has been
established by chemical analysis and
serves as a reference material for a
titrimetric analysis.

Gravimetric Analysis
In Gravimetry the analyte is
separated from a solution of the
sample as a precipitate.

Gravimetric Titrimetry
In gravimetric titrimetry, the mass of
a reagent of known concentration
required to react completely with
unknown is determined in terms of
mass.

Precipitation Titrations
Desirable properties of analytical
precipitates:
Readily filtered and purified
Insoluble - preventing losses during
filtration and washing
Stable final form (un reactive)
Definite composition after drying or
ignition

Gravimetric Analysis
Why?
Simple
Often required for high precision

How to Perform a Successful

Gravimetric Analysis
What steps are needed?
1.
2.
3.
4.
5.
6.
7.
8.
9.

Sampled dried, triplicate portions weighed

Preparation of the solution
Precipitation
Digestion
Filtration
Washing
Drying or igniting
Weighing
Calculation

Gravimetric Analysis
Precipitation Techniques
Add precipitating reagent to sample solution
Reacts with analyte to form insoluble
material
Precipitate has known composition or can
be converted to known composition

Precipitate handling involves

Quantitative collection (no losses)
Isolation of pure product

Measure mass of precipitate

Calculation of original analyte content
(concentration)

Gravimetric Analysis
Precipitating reagents:
Selective
Ag+ + Halides (X-) AgX(s)

Ag+ + CNS- AgCNS(s)

Specific
Dimethylglyoxime (DMG)
2 DMG + Ni2+ Ni(DMG)2(s) + 2 H+

Gravimetric Analysis
Filterability of Precipitates:
Colloidal suspensions
10-7 to 10-4 cm diameter
Normally remain suspended
Very difficult to filter
Crystalline suspensions
> tenths of mm diameter
Normally settle out spontaneously
Readily filterable

Gravimetric Analysis
Filterability of Precipitates:
Precipitate formation affected by
RELATIVE SUPERSATURATION(R.S.)

R.S. = (Q-S)/S
S = Equilibrium Solubilty of Precipitate
Q = Instantaneous Concentration

Larger Q leads to colloidal

precipitates.

Important Factors for Gravimetric

Analysis
Nucleation
Individual ions/atoms/molecules join
to form nuclei

Particle Growth
Condensation of
ions/atoms/molecules with existing
nuclei forming larger particles which
settle out

Colloidal Suspension
Colloidal particles remain suspended
due to adsorbed ions giving a net +
or - charge

Important Factors for Gravimetric Analysis

Coagulation, agglomeration
Suspended colloidal particles join to form
larger filterable particles.

Important Factors for Gravimetric

Analysis
Co-precipitation
Normally soluble compounds carried
down with insoluble precipitate
(surface adsorption, occlusion, mixed
crystals, entrapment)
Adsorption at the surface of particles
Occlusion of foreign substances during
crystal growth

Important Factors for Gravimetric

Analysis

Digestion
Precipitation heated for hour(s) in
contact with solution form which it
was formed

During
Duringdigestion
digestionat
atelevated
elevatedtemperature:
temperature:
Small
Smallparticles
particlestend
tendto
todissolve
dissolveand
andreprecipitate
reprecipitateon
onlarger
largerones.
ones.
Individual
Individualparticles
particlesagglomerate.
agglomerate.Adsorbed
Adsorbedimpurities
impuritiestend
tendto
togo
go
into
intosolution.
solution.

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

Fig. Ostwald ripening.

Cl
Cl-adsorbs
adsorbson
onthe
theparticles
particleswhen
whenininexcess
excess(primary
(primarylayer).
layer).
AAcounter
counterlayer
layerof
ofcations
cationsforms.
forms. The
Theneutral
neutraldouble
doublelayer
layercauses
causesthe
thecolloidal
colloidal
particles
to
coagulate.
particles to coagulate.

Washing
Washingwith
withwater
waterwill
willdilute
dilutethe
thecounter
counterlayer
layerand
andthe
theprimary
primarylayer
layercharge
chargecauses
causesthe
the
particles
to
revert
to
the
colloidal
state
(peptization).
particles to revert to the colloidal state (peptization).
So
Sowe
wewash
washwith
withan
anelectrolyte
electrolytethat
thatcan
canbe
bevolatilized
volatilizedon
onheating
heating(HNO
(HNO3).
).
3

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

Important Factors for Gravimetric

Analysis
Post precipitation
Precipitation that occurs on the surface of
the first precipitation after its formation.
Occurs with less soluble substances which
form super saturated solutions They
usually have an ion in common with the
primary precipitate.
E.g. Calcium oxalate precipitation is
contaminated by Mg-oxalate. Longer the
contact higher the contamination.

Organic
Organicprecipitating
precipitatingagents
agentsare
arechelating
chelatingagents.
agents.
They
Theyform
forminsoluble
insolublemetal
metalchelates.
chelates.

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

Gravimetric Analysis
Calculations of analyte content
requires knowledge of :
Chemistry
Stoichiometry
Composition of precipitate

Gravimetry and Solution

Equiliria
Thermal Conversion to Measurable Form
Removal of volatile reagents & solvent
Extended heating at 110 to 115 OC
Chemical conversion to known stable form

CaC2O4(s) CaO(s) + CO(g) + CO2(g)

Volatilization & trapping of component

NaHCO3(aq)+ H2SO4(aq) CO2(g)+ H2O +

NaHSO4(aq)

Gravimetric Calculations
Gravimetric Factor (GF):
GF = g analyte/g precipitate
% analyte = (weight analyte (g)/ weight
sample (g)) x 100%
% (w/w) analyte (g) = ((wt ppt (g) x GF)/wt
sample) x 100%

Gravimetric Errors
Unknown Stoichiometry:
Consider Cl- determination with
AgNO3
Ag+ + Cl- AgCl
Ag+ + 2 Cl- AgCl2

Gravimetric Errors
Co-precipitation: (w/AgCl)
Co-precipitant

Error

Rationale

NaF

Positive

All NaF is excess

NaCl

Negative

Fwt Na<Ag

AgI

Positive

All AgI is excess

PbCl2 (fwt 278.1) Negative

Gravimetric
Factors decreases

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

Alternative Gravimetry
Technique
How?
(OH-) by urea decomposition
(NH2)2CO CO2 + NH3

p412 vog

(S=) by thioacetamide decomposition

CH3CSNH2 H2S + CH3CONH2

(DMG) from biacetyl + hydroxylamine

CH3C(=0)-C(=0)CH3 + 2 H2NOH DMG + 2
H2O