CHEM 262: GRAVIMETRIC AND ELECTROANALYTICAL

METHODS I

COURSE LECTURER
E.E. Kwaansa-Ansah
Dept. of Chemistry, KNUST.
 COURSE OUTLINE
• GRAVIMETRIC METHODS OF ANALYSIS
Introduction:- Definition, types of Gravimetric methods
(Precipitation and Volatilization), criteria for successful
gravimetric analysis.
Steps in a Gravimetric Analysis:-Preparation of the solution,
Precipitation (types of precipitates), Digestion (impurities in
precipitates), Filtration,
Washing, Drying or ignition (thermogravimetry and combustion
analysis), Weighing, Calculation (gravimetric factor).
Organic Precipitants: Advantages and Disadvantages.
 COURSE OUTLINE
Precipitation from Homogenous solutions:- Precipitation
by urea hydrolysis, precipitation of sulphates,
precipitation of phosphates.
ELECTROANALYTICAL METHODS
Introduction:- Definition, advantages and disadvantages,
electrogravimetry.
Coulometry:- Definition, advantages, types of
coulometric methods, instrumentation and applications.
Potentiometry:- Definition, instrumentation, types of
electrodes and their applications.
 Definition
• The term GRAVIMETRY pertains to a Weight Measurement.
• Gravimetric method is one in which the analysis is completed
by a weighing operation.
• Gravimetric Analysis is a group of analytical methods in
which the amount of analyte is determined by the
measurement of the mass of a pure substance containing the
analyte.
• Gravimetric Methods can also be defined as quantitative
methods based on determining the mass of a pure
compound to which the analyte is chemically related.
 Definition
A) PRECIPITATION
• A chemical reaction causes the formation of a sparingly
soluble substance that precipitates from solution filtered,
washed, purified (if necessary) and weighed.
B) VOLATILIZATION
• In this method the analyte or its decomposition products
are volatilised and then collected and weighed, or
alternatively, the mass of the volatilised product is
determined indirectly by the loss of mass of the sample.
 For a successful determination in gravimetric analysis the following
criteria should be met

1)The desired substance must be completely precipitated. In

most determination the precipitate is of such low solubility
that losses from dissolution are negligible. An additional
factor is the common ion effect, this further decrease the
solubility of the precipitate.
E.g. When Ag+ is precipitated out by addition of Cl-
Ag+ + Cl- = AgCl
The low solubility of AgCl is reduced further by the
excess of Cl- which is added to force the reaction to proceed
towards right side.
For a successful determination in gravimetric analysis the
following criteria should be met

2)The weighed form of the product should be of known

composition.
3)The product should be pure and easily filtered. It is
usually difficult to obtain a product which is pure or
which is free from impurities. This could be reduced by
careful precipitation and sufficient washing.
Steps of a Gravimetric Analysis
• PREPARATION OF THE SOLUTION
• PRECIPITATION
• DIGESTION OF THE PRECIPITATE
• FILTRATION AND WASHING OF THE PRECIPITATE
• DRYING AND IGNITION OF PRECIPITATE
• WEIGHING OF THE DRY PRECIPITATE
• USING THE GRAVIMETRIC FACTOR FOR
CALCULATIONS.
 Preparation of the solution
• Some form of initial separation may be necessary to eliminate
interfering materials.
• The solution conditions must also be adjusted to maintain low
solubility of the precipitate and to obtain the precipitate in a form
suitable for filtration.
• Proper adjustment of the solution condition prior to precipitation
may also mask potential interferences.
Factors that must be considered include
• The volume of the solution
• The concentration range of the test substance
• The presence and concentration of the other constituents
• The pH of the solution
Preparation of the solution
• Usually, the precipitation reaction is selective for the
analyte.
• The pH is important because, it often influence the
solubility of the precipitate and the possibility of
interference from other substances.
• By adjusting the pH, substances may be selectively
precipitated
Formation of Precipitates
• During the precipitation process, the precipitant is added into
the analyte solution or generated insitu.
• Super saturation occurs, followed by nucleation and
precipitation.
• Nucleation is a process whereby a minimum number of
particles come together to produce microscopic nuclei of the
solid phase.
• The higher the degree of super saturation, the greater the rate
of nucleation. The formation of a greater number of nuclei unit
time will ultimately result in more total crystals of smaller size.
• The diameter of the tiny particles must be at least 10-4 mm
before it will settle from solution as a precipitate.
 Formation of Precipitates
• The sequence of precipitate formation is;

• Ions in solution Colloidal Particles Precipitate

• The nucleation is followed by particle growth in which the small
tiny particles increase in size to become relatively large particles.
• Prior to nucleation, there is an induction period which depends on
or varies with the type of precipitate.
• When nucleation occurs, the nuclei formed grow in size easily
than for more nuclei to form because the cations and anions in
solution attach themselves to the surface of the nuclei by
chemical bonding. This results in growth of a three dimensional
crystal lattice
Conditions for Analytical Precipitation

• In general, on analytical precipitate for gravimetric

analysis should;
• Consist of perfect crystals large enough to be filtered
and washed.
• Be free from impurities within
• Present a minimum surface area for the adsorption of
impurities without.
• Be insoluble enough that loss of precipitate due to
solubility would be negligible
Types of Precipitate

•There are 3 main types of precipitate

Curdy Precipitate
Gelatinous Precipitate
Crystalline Precipitate
 Curdy Precipitate
• The cations and anions reacts to form a soluble colloid and the
grow in size (coagulate) to filterable sized particles. The
common and useful ones are the halides of Silver (AgCl, AgBr
and AgI).
• The particles initially precipitate as suspended, colloidal
particles that do not grow up to a large enough size to
precipitate. The impurities on the surfaces of the tiny particles
can normally be washed off, since the particles are not firmly
bound to one another and the wash liquid can penetrate to all
parts of the curd.
• Usually, heating and allowing the precipitate to stand for 1 and
2 hours in contact with the mother liquor promotes coagulation
of the colloidal particles.
 Gelatinous Precipitate
• The formation is the same as that of the curdy precipitate. The
primary particle of a gelatinous precipitate is much larger in
number and of much smaller dimensions than those of
crystalline or curdy precipitate.
• Typical examples are the +3 metal hydroxide e.g. Fe(OH)3,
Al(OH)3. The gelatinous precipitate adsorbs or traps a lot of
water molecules and impurities to itself.
• Washing and re-precipitation can be employed to increase the
purity of a gelatinous precipitate once it has been formed.
• Digestion is not beneficial, since the precipitate is so slightly
soluble that the particles have little tendency to grow in size.
 Crystalline Precipitate
• They are more easily handled than curdy and gelatinous
precipitates. The size of the individual particle can be varied to a
degree. A crystalline precipitate such as BaSO4 sometimes adsorbs
impurities when the particles are small. As the particles grow in
size, the impurity may become enclosed in the crystal. This type of
impurities cannot be removed by washing the precipitate.
• After a crystalline precipitate is formed, the analyst can still
increase the purity. If the substance can be readily redissolved, it
can be filtered, redissolved and re-precipitated. The contaminating
ion will be present in a lower concentration during the second
precipitation and consequently a smaller amount will be co-
precipitated
 Factors that determines Particle Size of Precipitates

• Von Weimarn discovered that the particle size of

precipitates is inversely proportional to the relative
supersaturation of the solution during the precipitation
process:
• Relative Supersaturation = (Q – S)/S Von Weimarn Ratio
Factors that determines Particle Size of Precipitates
• Where Q is the concentration of the mixed reagent
before precitation occurs (is the degree of
supersaturation).
• S is the solubility of the precipitate at equilibrium.
• When Relative Supersaturation is large, the precipitate
tends to be colloidal (Curdy and Gelatinous).
• When Relative Supersaturation is low on the average,
the precipitate tends to be crystalline.
• For the best possible precipitate, conditions should be
adjusted so that Q will be as low as possible and S will
be relatively large.
The steps commonly employed to maintain favourable
conditions for precipitation
• Precipitation from dilute solution. This keeps Q low.
• Adding dilute precipitating reagent slowly, with effective stirring. This
also keeps Q low. Local excesses of the reagent are prevented by
stirring.
• Precipitation from hot solution. This increases S. the solubility should
not be too great or the precipitation will not be quantitative. The
bulk of the precipitation may be preformed in the hot solution, and
then the solution may cooled to make the precipitation quantitative.
• Precipitate at as low a pH as is possible to still maintain quantitative
precipitation. As shown above, many precipitates are more soluble in
acidic medium and slows the rate of precipitation. They are more
soluble because the anion of the precipitate combines with protons
in solution
 Digestion of Precipitates
• Digestion is a process of allowing the precipitate to stand in contact
with the mother liquor frequently at elevated temperatures for
sometime before filtration. The process is also called Ostwald
Ripening and it yields a product with improved purity and
filterability.
• The small particles tend to dissolved and re-precipitate on the
surfaces of a larger crystals. During these processes, many pockets
of imperfection become exposed to the solution, the contaminant is
hence able to escape from the solid and more perfect crystals
result. Also absorbed or trapped impurities tend to go into solution.
• Digestion is usually done at elevated temperatures to purity of
precipitates.
 Types of Colloidal Precipitates
• LYOPHILIC AND LYOPHOBIC PRECIPITATES
• Some precipitate particles as they settle down from solution
carry a large quantity of solvent. Such materials are termed
as GELS.
• Lyophilic precipitates are those with strong affinity for the
solvent. Such precipitate are also called EMULSOID
• If water is the solvent, then the precipitate is referred to as
Hydrophilic precipitate e.g. Al(OH)3 and Silicic acid.
• Lyophobic Precipitates are those with only little affinity for
solvent. They are also called SUSPENSOID
 Colloidal ppt
• When coagulation takes, very little solvent is retained. If water is the
solvent, then it is called Hydrophobic precipitate e.g. AgCl
• Coagulation of a hydrophilic colloid, such as hydrous Ferric oxide
(Fe2O3.xH2O) is more difficult and it produces a gelatinous precipitate
that is difficult to filter because it tends to clog the pores of the filter.
Gelatinous precipitate adsorbs impurities readily because of their
very large surface area.
• Reprecipitation is required and during the process, the concentration
of impurities in solution become reduced to a low level and
adsorption will be very small.
• Coagulation of a hydrophobic colloid is fairly easy and results in a
curdy precipitate. Despite the colloidal nature of AgCl, the
gravimetric determination of chloride is one of the most accurate
determinations.
 Impurities in Precipitates
• Impurities usually enter or contaminate precipitates by the
process of co-precipitation. The process where by
precipitates tends to carry down from the solution other
constituents that are normally soluble contaminating the
precipitate is called co-precipitation.
• There are 3 main ways by which foreign material may be co-
precipitated.
• Occlusion and Inclusion
• Surface adsorption
• Post precipitation
 Occlusion and Inclusion
• Occlusion is the trapping of impurities inside the precipitate.
E.g. H2O may be trapped in pockets when AgNO3 crystals are
formed. This can be expelled by melting the crystal.
• During precipitation the trapped water may contain dissolved
impurities.
• Inclusion occurs when ions, generally of similar size and charge
are trapped within the crystals lattice of a precipitate. E.g.
isomorphous inclusion of K+ in NH4MgPO4 in precipitation.
• NB; two compounds are said to be isomorphous if they have
same type of formula and crystallize in similar geometric
forms.
Occlusion and Inclusion
• Occluded or included impurities are difficult to
remove.
• Digestion may help but it is not completely effective.
Washing cannot also remove the impurities.
• However, purification by dissolution and re-
precipitation may be helpful.
 Post precipitation
• Sometimes when a precipitate is allowed to stand in contact with
the mother liquor, a second substance will slowly form a precipitate
with the precipitating reagent. This is called Post precipitation.
• E.g. when CaC2O4 is precipitated in the presence of Mg2+, MgC2O4
does not immediately a precipitate because it tends to form a super
saturated solution. MgC2O4 will come down if the solution is allowed
to stand too long before filtration.
• When two ions are isomorphous, one ion can replace another in a
crystal, resulting in a mixed crystal.
• The process is called isomorphous replacement. This form of
contamination is very serious and little can be done about it and
precipitates in which this occurs are seldom used analytically
 Washing and filtering of precipitates
• The aim of washing is to remove one or more soluble compounds.
Surface impurities may be removed by washing the precipitate and
filtering it off. Loses may be reduced by using a minimum of wash
solution. The following expression may be used;
• Xn = X0[U÷ (U+V)]n
• Where Xo = the concentration of the impurity before washing
Xn = the concentration of the impurity after n washing
U = the volume of the liquid used in the washing
V = the volume of the liquid remaining with the precipitate after
draining.
Washing and filtering of precipitates
It is advisable to wash with small amount of solvent at a time for a
number of times to remove the impurities than to use large volumes
for few washes.
• Many precipitates cannot be washed with pure water, because
peptization occurs. When a precipitate is washed, a test should be
made to determine when the washing is complete. Frequent
qualitative test must be made upon portions of the filtrate for some
foreign ions known to be present. The absence of the ions in the
washing dictates whether the washing should cease or continue.
• To prevent peptization, an electrolyte must be added to the washed
solution such as HNO3.
• The electrolyte must be one that is volatile at the temperature to be
used for drying or ignition and must not dissolve the precipitate.
 Drying or Ignition of the precipitate

• After filtration, a gravimetric precipitate must have a

constant weight. To achieve that it must be heated.
• The heating serves a dual purpose;
• To remove the solvent and volatile electrolytes carried down
with the precipitate
• To induce chemical decomposition to give product of known
composition
Types of Drying

• Ambient temperature/ Room temperature

• Some precipitate can be dried sufficiently for analytical
work by air drying. It can be dried by just washing the
precipitate with ether of ethanol and blowing air over it.
E.g. MgNH4PO4.6H2O.
• Low temperature
• Some precipitate loose water readily in an oven at
temperatures of 110-1200C for about 1 to 2 hours. These
are usually precipitate washed with water. E.g. AgCl
 Ignition of precipitate

• It is heating of precipitate at very high temperatures far

above 2500C.
Purposes.
• To remove occluded or very strongly absorbed water
molecules. E.g. gel. Precipitate such as the hydrous oxides
of Fe and Al absorbs water quite strongly and must be
heated to very high temperature to remove water
completely.
• To convert the compound completely from one form to the
other that can be handled gravimetrically
 Ignition of precipitate
• E.g. CaC2O4 heat CaCO3 + CO heat CaO + CO2
This analysis is referred to as Thermogravimetry

• Thermogravimetry is a form of gravimetric analysis where

mass is measured as a function of temperature:
 Gravimetric Calculations

Substance weighed ppt Substance sought G.F.

BaSO4 S (S) ÷ M.BaSO4

Fe2O3 FeO (2FeO) ÷ Fe2O3

PbCrO4 Cr2O3 (Cr2O3) ÷ 2 PbCrO4

KClO4 K (K) ÷ KClO4

KClO4 K2O (K2O) ÷ (2 KClO4)

Fe2O3 Fe3O4 (2Fe3O4) ÷ (2 Fe2O3)

SiO2 KAlSi3O3 (KAlSi3O3) ÷ (3 SiO2)

 Example 1
• A 0.3516 g sample of commercial phosphate detergent was ignited at a red
heat to destroy the organic matter. The residue was then taken up in hot
HCl which converted P to H3PO4. The phosphate was precipitated with Mg2+
followed by aqueous NH3 to form MgNH4PO4.6H2O. After being filtered and
washed, the precipitate was converted to Mg2P2O7 (Mr = 222.57) by ignition
at 1000oC. This residue weighed 0.2161 g. Calculate the percent P in the
sample.
Solution:
Gravimetric factor, GF = Mr. of substance sought / Mr. of substance
substance weighed x a/b (mol sought / mol weighed)
GF = 30.974 g / 222.57 g x 2/1 = 0.278
Amount of P = GF (0.278) x Wt. of precipitate (0.2161) = 0.0601g
% P = 0.0601 g P / 0.3516 g sample x 100 = 17.11%
 Example 2
• A 0.4960 g sample of a CaCO3 is dissolved in an acidic solution.
The calcium is precipitated as CaC2O4.H2O and the dry precipitate
is found to weight 0.6186 g. What is the percentage of CaO in the
sample? (Mr CaO = 56.08; Mr CaC2O4.H2O = 146.2)
Solution:
GF = 56.08 g / 146.12 g x 1/1 = 0.3838
Wt of CaO = Wt. of ppt. x GF = 0.6186 g x 0.3838
= 0.2374 g
% of CaO in CaCO3 = 0.2347 g / 0.4960 g x 100
= 47.87%
PRECIPITATION FROM HOMOGENOUS SOLUTION
• It is a gravimetric technique in which the precipitating
agent/precipitant is not added into the solution of the
analyte, but rather slowly generated by means of chemical
reaction within the solution (insitu).
• When a precipitant is added to a solution there would
always be some local regions of high concentration.
The most favourable conditions for precipitation involve
precipitating from dilute solution and adding the
precipitating agent slowly with effective stirring to maintain
low supersaturation. Homogenous formation of the
precipitating agent minimizes surpersaturation.
PRECIPITATION FROM HOMOGENOUS SOLUTION
• This method leads to both large and pure precipitates. By
varying the rate of the chemical reaction which produces
the precipitates in homogenous solution, it is possible to
alter the physical appearance of the precipitate.
• During the slow growth, the particles have time to attain a
large size without imperfections.
• Therefore the amount of occluded impurities is minimized.
 Precipitation by means of Urea Hydrolysis
(Precipitation of hydroxides)
• Urea is very useful reagent for the precipitation of certain
substances whose solubility is affected by pH. It is used to
precipitate metal ions that form insoluble hydrous oxides
(hydroxides) or oxides of weak acids.
• NH2CONH2 + H2O heat 2NH3 + CO2
• The hydrolysis is slow at room temperature but very rapid
at about 100oC. Hence the pH of the medium can be
controlled in effecting precipitation by controlling the
temperature and duration of heating.
 Homogenous Precipitation of Phosphate
• The phosphate may be precipitated with the phosphate
ions derived from trimethylphosphate by stepwise
hydrolysis.
• (CH3)3PO4 + 3H2O heat 3CH3OH + H3PO4
• Other metal precipitated this way are Hf, Zr.
Homogenous Precipitation of Oxalate
• Urea may be employed to raise the pH of an acidic
solution of HC2O4- ion. From this, metal ions such as
Ca, may be precipitated in a dense form.
• NH2CONH2 + 2HC2O4- + H2O 2NH4+ + CO2 +
C2O42- Ca CaC2O4.
• In this reaction, ethyloxalate (C2H2)2C2O4 can be
hydrolyzed to serve as a reagent for oxalate ion.
Metals precipitated this way are Ca, Mg and Zn. For
this precipitation of Th, the methyloxalate is used.
 Homogenous Precipitation of Sulphates
• The sulphate ions may be generated by the hydrolysis of
sulphamic acids.
• NH2SO3H + H2O NH+4 + H+ + SO42-
• The hydrolysis of dimethylsulphate can also provide the
SO42- ions for the precipitation of Ba, Ca, Pb, Sr.
Factors Which Affects Solubility of Precipitates
• Temperature
• Nature of solvent
• Presence of other ions (common ion effect)
• pH of the medium
Temperature
• The solubility of the precipitate increases with rise in
temperature.
• For some precipitate, the effect of temperature is
small and for others is appreciable.
• E.g. The solubility of AgCl at 10 and 100OC are 1.72
and 21.1mgL-1 respectively. Also for BaCl2, it is 2.2 and
3.9mgL-1 at 10 and 100oC respectively.
Nature of Solvent

•Most inorganic salts are more soluble in water

than in organic solvents (like dissolves like).
• The reason is that water has a large dipole
moment and is both attracted to cations and
anions to form hydrated compounds.
Common Ion Effect
• A precipitate is generally more soluble in pure
solvents (water) than in a solution which contains one
of the ions of the precipitate.
Example
Calculate the molar solubility of CaF2 in
1. pure water
2. 0.01M CaCl2
3. 0.01M NaF solution
Ksp CaF2= 4×10-11 neglecting the hydrolysis of the F-
ion.
pH of the Medium
• The solubility of a salt of a weak acid depends on the pH
of the solution. Some of the more important examples of
such salts are C2O4-2-, S2-, OH-, CO32- and PO43-.
• Reason: H+ ions combine with anion of the salt to form
the weak acid thereby enhancing the solubility of the
salt.
Example: The pH at which the ff compounds begin to
precipitate if the solution is 0.1M in each cation.
• FeOH3, Ksp= 1.5 ×10-36
• Mg(OH)2, Ksp = 5.9 ×10-12
 ORGANIC PRECIPITANTS
• They are organic reagents which forms sparingly soluble and
coloured compounds with inorganic ions.
• They usually have high molecular weight so that a small amount of
the ions will produce large precipitates.
• Some of the organic precipitants are useful not only for
precipitation but also for solvent extraction. Most of these
precipitants combine with cations to form chelate rings.
• Generally most of the organic precipitants which form chelate
compounds contain both acidic and basic functional groups. The
metal ion interacts with these groups and then form a heterocyclic
rings.
Examples
8-hydroxyquinoline (oxine)
8-hydroxyquinaldine
Nitrosophenylhydroxylamine (Cupferron)
α-nitroso-β-naphthol
Dimethylgloxime
Pyrogallol
Salicyladehyde oxime
α- Benzoin Oxime (Cupron)
Quinaldic acid
Arsonic acid
Tetraphenylarsonium chloride
Sodiumtetraphenylboron
NB: Look out for the metals that each can precipitate
Advantages of Organic Precipitants
• They are insoluble in water hence the metal ions can
quantitatively be precipitated.
• The organic precipitate often have high molecular weight hence
a small amount of metal may yield a large weight of precipitate
minimising weighing errors.
• Some of the organic reagents are fairly selective yielding
precipitate with only a limited number of cations.
• They often form coarse and bulky precipitates which are easily
handled.
• They can be used for the indirect titrimetric method for the
determination of metals.
Disadvantages of Organic Precipitants
• Many of the chelate compounds do not have good
weighing forms and only used for separations and not
determinations.
• There is a danger of contaminating the precipitate
with the chelating agent because of its limited
solubility in water.
 Application of Gravimetric Analysis
1. Elemental Analysis:
The results obtained from the analysis are used in the determination of
• Empirical formula
• Molecular formula
• Structural formula
• Analysis of organic compounds can easily be done gravimetrically by burning
the organic sample in a stream of oxygen. The carbon comes out as CO2 and
hydrogen as H2O. Through this, the amount/% C and H can be estimated.
2. Separation Analysis:
Mean of separating a substance from a mixture by dissolution and precipitation.
3. Environmental and Health Analysis:
Determination of levels of toxic substances.
ELECTROCHEMISTRY
• It involves
• The use of electric current to cause chemical change
as in electrolyte cells. The process is referred to as
electrolysis.
• The generation of electric current by the use of
chemical change as in Galvanic or voltaic cells.
 ELECTROGRAVIMETRY
In this process the element to be determined is deposited
electrolytically upon a suitable electrode. Hence filtration is
avoided and co-deposition is very rare. It is governed by
• The Ohm’s law
• Faraday’s laws
Ohm’s law: it states that the current, I, flowing through a
circuit is directly proportional to the potential difference or
electromotive force applied.
EαI
E = IR or V= IR
 ELECTROGRAVIMETRY
• Faraday’s laws:
1. The amount of substance deposited or liberated at an electrode in
a cell during electrolysis is directly proportional to the quantity of
electricity passed through the solution.
M = Ait / VF
2. The amount of different substances which are deposited or
liberated by the passage of the same quantity of electricity through
different electrolytes arranged in series are directly proportional to
their chemical equivalence.
• MA/ CEA = MB/CEB
• C.E = Atomic weight / charge of the ion.
 Terms used in Electrogravimetry
• Coulomb: it is the quantity of electricity passing when 1 ampere flows for
1 second.
• Electrochemical Equivalence: It is the weight of an element liberated by
the passage of one coulomb of electricity.
It is found experimentally that 96485C is required to liberate one
equivalent of any substance of any metal. This quantity of electricity is
called the Faraday constant F.
• Current Density: It is the current per area of the electrode surface. It is
expressed in Ampere per cm2 or A/dm2 of the electrode surface.
• NB: Very high or low current densities should be avoided since it does not
yield favourable deposits. Moderately high current densities give more
satisfactory deposits.
 Terms used in Electrogravimetry

• Current Efficiency: It is the ratio of the actual amount of a

particular substance that is deposited to that obtained
theoretically from calculation using the Faraday’s laws.
• Decomposition potential: It is the minimum external
voltage that must be applied to bring about continuous
electrolysis.
Why does Voltage change when current flows through a cell.
For a cell to do useful work or for electrolysis to occur
significant current must flow. Whenever current flows, three
factors decrease the magnitude of the out put voltage of a
galvanic cell and increase the magnitude of the applied
voltage needed for electrolysis.
The factors are the
• Ohmic potential
• Concentration polarization
• Overpoatential
 OHMIC POTENTIAL
It is the voltage needed to force current to flow through a cell.
Any cell has some electric resistance. If current is drawn from a
cell, the output voltage decreases because part of the energy
released by the chemical reaction is needed to overcome
resistance inside the cell. The voltage applied to an electrolytic
cell must be great enough to drive the chemical reaction and
to overcome cell resistance.
• EFFECTS OF OHMIC POTENTIAL
• Output of Galvanic cell. Egal = Enerst - IR
• Input to electrolytic cell Eelec = - ( ENerst + IR)
• Where ENerst = voltage of cell with zero current.
 CONCENTRATION POLARIZATION
• It occurs when the concentration of species created or
consumed at an electrode is not the same at the surface of
the electrode as it is in bulk solution.
• Concentration polarization decreases the magnitude of
voltage available from a Galvanic cell and increases the
magnitude of the voltage required for Electrolysis.
• Effects of Ohmic potential and concentration polarization
• Output of Galvanic cell: Egal = ENerst – IR - Econc
• Input to electrolytic cell: Eelec = - (ENerst +IR + Econc)
• Where Econc = the additional voltage
 CONCENTRATION POLARIZATION
To decrease Concentration Polarization
• Raise the temperature
• Increase stirring rate
• Increase electrode surface area
• Change in ionic strength to raise or decrease attraction
between the electrode and the reactive ion.
 OVERPOTENTIAL
It is the difference between the expected voltage (after accounting for
IR drop and conc. Polarization) and the observed voltage. Even when
conc. Polarization is absent and Ohmic potential is taken into account,
some electrolyses require a greater than expected voltage and some
galvanic cells produce less voltage than anticipated.
The faster you wish to drive an electrode reaction, the greater the
overpotential that must be applied. Over potential can be traced to the
activation energy barrier for electrode reaction.
• Effects of Ohmic potential, conc polarization and Overpotential
• Output of Galvanic cell: Egal = ENerst – IR - Econc - Eover
• Input to electrolytic cell: Eelec = - (ENerst +IR + Econc + Eover)
 Polarized Electrodes.
•An electrode is polarized if its potential deviates from
reversible or the equilibrium value.
•An electrode is said to be depolarized if the amount
of polarization is lowered by a substance.
•NB
Ohmic potential, concentration polarization and
overpotential is always to increase the magnitude of
the applied voltage for electrolysis.
 ELECTROGRAVIMETRIC ANALYSIS
The analyte is electrolytically deposited as a solid on
the electrode. The increase in the mass of the
electrode tells us how much analyte was present.
Test for Completion of the Deposition
•Disappearance of colour of solution
•Deposition on freshly exposed electrode surface
•Qualitative test for Analyte in solution.
 Characteristics an of Deposit from Electrogravimetry
The ideal deposit for Analytical purpose should be
• Adherent
• Dense
• Smooth on this electrode
In this form, it is readily washed without loses.
Flaky, Spongy, powdery or granular deposits adhere loosely
to the electrodes and for this and other reasons, this type of
deposit should be avoided
 How to Achieve or obtain Ideal deposit
• When the metal/analyte is deposited from a solution in which it is
present as a complex ion rather than as a simple ion. E.g. [Ag(CN)2]-,
[Ni(NH3)6]2+
• Mechanical stirring. This reduces concentration gradient and
concentration polarization.
• Increased current density. Increased C.D up to a certain critical value
will lead to a decrease in grain size of the deposit. Beyond that value
deposits tend to be unsatisfactorily.
• Increased temperature: Raising the temperature to about 70-80°c
improves the physical properties of the deposits.
• Addition of cathode Depolarizer: this reduces the evolution of gases
such as H2, O2 at the electrode. E.g. of such depolarizer are HNO3 or
(NH4)NO3.
 COULOMETRIC METHODS ANALYSIS
It is based on counting the number of electrons used in a
chemical reaction. There is a direct proportionality between
the amount of electricity and the amount of REDOX reaction
that occur when current passes through an electrolyte.
• Coulometric methods are based on measurement of the
number electrons that participate in a chemical reaction.
• It is simple in principle and relatively uncomplicated in lab
application.
• The major problem is to ensure that all the electricity passed
through the cell is associated with the desired electrode
reaction.
 TYPES OF COULOMETRY

Constant potential

Constant current
 Constant Potential Coulometry
• Is, more selective than constant current coulometry. In
controlled potential coulometry, current decreases
exponentially as analyte concentration decreases. Because
current is not constant charge is measured by integrating the
current over the time of the reaction.
• Q=0 ∫t Idt
• The equivalence point is never reached because the current
decays exponentially. However, the equivalence point can be
approached by letting the current decay to an arbitrary set
value.
 Constant Potential Coulometry
• The procedure is to adjust the potential difference between
the cathode and the reference electrode to a desired value.
• An obvious way to prevent the intrusion of an undesired
electrode reaction is to control the potential of the electrode.
This will require three electrodes in the solution [cathode,
anode and reference electrode and a potentiostat to control
the potential of the electrode at which the desired reaction
occurs.
• The electrode where the reaction of interest occurs is called
the WORKING ELECTRODE.
 Constant Potential Coulometry

• As electrolysis proceeds, the cathode tends to become more

negative with respect to the reference.
• This is restored by re-adjusting the rheostat.
• The ammeter reading decreases throughout the electrolysis
and reaches a low constant value indicating the end of the
electrolysis.
 CONSTANT CURRENT COULOMETRY
[COULOMETRIC TITRATION]
• Coulometry at constant potential is applicable only to a
limited number of substances which undergo quantitative
reaction at an electrode during electrolysis.
• The constant current coulometry has extended scope to
include those that do not react quantitatively at an electrode.
• Constant current electricity is employed to generate a
reagent which reacts stoichiometrically with the substance
to be determined.
• The quantity of the substance reacted is calculated with the
aid of the Faraday’s laws.
CONSTANT CURRENT COULOMETRY

•The quantity of electricity passed can be evaluated

simply by timing the electrolysis at constant
current.
•In coulometric titration, the reagent is generated
electrically and its amount is evaluated from the
knowledge of the current and the generating time.
 INSTRUMENTAION

•The apparatus is made up of

•i) A coulometer
•ii) A controlled source of current
•iii) The electrolytic vessel
INSTRUMENTAION
• COULOMETERS-They are devices in which the
reagents for the reaction are generated.
• TYPES OF COULOMETERS
• Silver Coulometer
• Iodine Coulometer
• Hydrogen-Oxygen gas Coulometer
• Hydrogen-Nitrogen gas Coulometer
 TYPES OF COULOMETERS
• Silver Coulometer:
• The silver coulometer is the most accurate and is made up of
a Pt basin which serves as the cathode and the anode is a
silver rod. The electrolyte is 10% AgNO3 solution.

• Iodine Coulometer:
• The iodine coulometer is made up of a pair of Pt electrodes
immersed in KI solution. At the end of the determination the
liberated iodine is titrated with standard thiosulphate
solution and with this the number of coulombs passed can
be calculated.
 TYPES OF COULOMETERS
• Hydrogen-Oxygen gas Coulometer:
• The hydrogen-oxygen gas coulometer consist of a tube of about
40cm in length and 2cm in diameter. The electrolyte is 0.5M
solution of K2SO4 which is saturated with O2 and H2 gases prior
to the experiment. When the volume of the gas is no more
increasing, its volume is read and corrected to s.t.p. The
hydrogen-oxygen gas coulometer yields a negative error at
small current densities.
• Hydrogen-Nitrogen gas Coulometer:
• The hydrogen-nitrogen gas coulometer has the same set up as
the H2-O2 coulometer except that the electrolyte is hydrazine
sulphate and free from this error
 REQUIREMENTS FOR COULOMETRY

• The requirements are that the reagent generating electrode

reaction should proceed with 100% efficiency and that the
generated reagent should react stoichiometrically and rapidly
with the substance being determined.
• The reagent may be generated directly within the test solution
or less frequently, it may be generated in an external solution
which is allowed to run continuously into the test solution.
• Since small quantity of electricity can be readily measured
with degree of accuracy, the method is highly sensitive.
ANALYTICAL APPLICATIONS OF COULOMETRY.
• Acid-base titration:
• The method has been used for both strong and weak acids. An advantage is
taken of the fact that electro reduction of water at a Pt cathode yields OH-
2H2O + 2e- → H2 + 2OH-
H+ can be generated at the anode and this is reacted with the base.
2H2O → O2 + 4H+ + 4e-
• Precipitation titration:
• Cl-, Br- and I- in solution can accurately be determined with
coulometrically generated Ag+ at the anode.
Ag → Ag + e-
ANALYTICAL APPLICATIONS OF COULOMETRY

• Complexometric titration:
EDTA is generated through reduction of the stable mercury
(II) EDTA amine complex at a mercury pool cathode in
ammonia/ammonium nitrate buffer.
HgNH3Y2- + NH4+ 2e- → Hg + 2NH3 + HY3-
As the EDTA is generated, it reacts rapidly with a metal ion to
form the EDTA complex. This reaction has been applied to the
titration of Ca2+, Ni2+ etc.
ANALYTICAL APPLICATIONS OF COULOMETRY
• Reduction oxidation titration:
A good example is the oxidation of Fe2+ to Fe3+
Fe2+ + Ce4+ → Fe3+ + Ce3+
• In a solution of Fe2+ an excess of Ce3+ is added. The Ce3+ is
oxidized at the anode to Ce4+ which in turn reacts
immediately with the Fe2+ ions as shown above.
• The end point occurs when the first excess of Ce4+ is
generated. As this can be detected potentiometrically.
 ADVANTAGES OF COULOMETRY
• It has higher accuracy because current and time can be
determined with exceptional precision
• Standard solutions are not required, but in their place the
coulomb becomes the primary standard.
• Unstable reagents (e.g. Br2, Cl2, Ag2+, Ti3+ etc) can be used
as titrants because they are generated and used immediately.
• It needs only very small amount of titrant
• Sample solution is not diluted in the internal generation
procedure.
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