REDOX TITRATIONS

Common REDOX Indicators

-based upon titrations with reducing or oxidizing agents
aA + bT c Product 1. Ferroin
OA RA RP OP -tris (1,10-phenanthroline) iron (II) sulfate
RA OA OP RP -one of the best indicators
-may be performed using visual indicators or by -useful for titrations with cerium (IV)
measuring the potential with an appropriate indicating -end point; red to pale blue
electrode to construct a potentiometric titration curve
-areas of applications food analyses, industrial 2. Diphenylaminesulfonic acid
analyses, and pharmaceutical analyses -used for titrations with dichromatic in acid
solution
Balancing of Redox Reaction -care must be taken in disposing of Cr (VI) since it
is an environmental pollutant that is carcinogenic
Oxidation Half-reaction -end point; colorless to purple
-increase in oxidation state
-loss of electrons Tirants: Oxidizing Agents
-reducing agent is oxidized
-oxidation product 1. Iodine
-hRA = # of e- loss -moderately strong oxidizing agent
-more selective than the strong oxidizing agents
Reduction Half Reaction -performed in neutral or mildly alkaline (pH 8) to
-decrease in oxidation weakly acid solutions
-gain of electrons -high-purity I2 can be obtained by sublimation
-oxidizing agent is reduced -usually standardized against a primary standard
-reduction product reducing agent such as As2O3
-hOA = # of e- gained -has a low solubility in water but the complex I3- is
very soluble
Visual Detection of Endpoint
Iodometric Method
1. Self-indication
-if titrant is highly colored, this color may be used Titrant Iodine Na2SO3
Analyte H2S, SO32-, Sn2+, Oxidizing agent
to detect the end point
As3+, N2H4 treated with an
-the end point does not occur at the equivalence excess of iodide
point, but a fraction of a drop beyond Indicator Starch Starch
-error is small (e.g. KMnO4) Titration Direct & Back Indirect Tiration
Method Titration
2. Starch Indicator
-used for titrations involving iodine
-iodo-starch complex which is a very dark-blue 2. KMnO4
color -widely used strong oxidizing titrant
-color reaction is very sensitive even to very small -acts as a self-indicator for end-point detection
amounts of iodine -can be standardized using primary standard
Na2C2O4
3. REDOX Indicators
-depends on the half-reaction potentials 3. K2Cr2O7
-highly colored dyes that are weak reducing or -slightly weaker oxidizing agent
oxidizing agents that can be oxidized or reduced -availability as a primary standard
-the colors of the oxidized and reduced forms are -used in the titration of iron (II)
different
-the REDOX indicator reaction must be rapid and
reversible for a sharp end point to be detected
4. Cerium (IV) Special Methods used in Pharmaceutical Analysis for
-powerful oxidizing agent Crude Drugs and Products derived from them
-salt of cerium (IV), (NH4)2Ce(NO3)6 as a primary
standard Purposes:
-ferroin is the suitable indicator for cerate -to establish purity
titrations -to determine the amount of therapeutically active
-can be prepared from (NH4)Ce(SO4)4 . 2 H2O and constituent present for the purpose of
CeO2 . 4 H2O standardization

5. KBrO3 Classification:
-primary standard form is available from 1. Chemical Methods
commercial sources 2. Biological Methods
-a convenient and widely used stable source of -measure the effects of drugs upon microbes,
bromine animals or animal tissues
-1 mol KBrO3 = 3 mol Br2
-used in the determination of organic compounds 1. Ash Determination
that react with bromine Ash
-bromine is incorporated into an organic -the residue remaining after incineration
compound either by substitution or by addition -represents the inorganic salts naturally occurring
in the drug and adhering to it
Titrants: Reducing Agent -may also include inorganic matter added for the
purposes of adulteration
1. Na2S2O3 -furnishes a basis for judging the identity and
-only common reducing agent that is stable to air cleanliness of a drug
oxidation -gives information relative to its adulteration with
-can be kept for long periods of time inorganic matter
-KIO3 is an excellent primary standard -Gravimetric Method

2. Iron (II) Temperature Equivalents (Electric Furnace)

-only slowly oxidized by air in sulfuric acid solution Description Temperature Range
-prepared from Mohrs salt and Oespers salt Very Dull-Red Heat 500 550oC
-can be used to titrate stron oxidizing agents such Dull-Red Heat 550 700oC
as cerium (IV), chromium (VI), and vanadium (V) Bright-Red Heat 800 1000oC
Yellow-Red Heat 1000 1200oC
3. Chromium (II) White Heat 1200 1600oC
-very powerful reducing agent but readily air- *careful control of temperature is the most
oxidized important analytical factor to regulate
-difficult to handle
-used in the titration of iron (III), copper (II), tin Total Ash
(IV), chromate, vanadate, and chlorate -residue remaining after incineration

4. Titanium (III) Data:

-very powerful reducing agent but readily air -mass of crude drug
oxidized -mass of total ash
-difficult to handle
-used for the titration of the oxidized forms of Acid Insoluble Ash
copper, iron, silver, gold, bismuth, uranium, and -part of the total ash which is insoluble in diluted
tungsten HCl
-consists almost entirely of the soil silica adhering
from the soil adhering to the drug
Data:
-mass of crude drug
 -mass of acid insoluble ash Extractives
-amount of a drug soluble in a given solvent
Residue on Ignition -index of purity
-expensive chemicals -gravimetric method
-yields negligible amount of ash -an approximate measure of the amount of a
certain constituent or group of related constituents
Loss on Ignition present in a drug
-technique which provides a means of determining
the percentage of test material which is volatilized Soxhlet Extraction Method
and driven off under the conditions specified -continuous extraction
-uses the same portion of solvent repeatedly
2. Water Determination -separation of the solvent and solute after the
-drugs official in the USP and NF contain varying extraction
quantities of water
-forms water in crude drugs Solvents:
1. Water of crystallization
2. Water in the adsorbed form 1. Absolute Ether
-to ensure uniformity in the official drugs -drugs which contain volatile oils (Total Ether-
Soluble Volatile Extractives
Data:
-drugs having active constituents associated with
-mass of crude drug
volatile matter (Non-Volatile Ether-Soluble
-mass of water or volume of water
Extractives
Methods
2. Alcohol
-drugs with Resinous Matter
1. Gravimetric Method
-for drug containing no constituents other
3. Diluted Alcohol
than water, volatile at 105oC
-method: intermittent agitation
-for drugs containing ether-soluble
constituents, volatile at 105oC
4. Water
-method: intermittent agitation
2. Azeotropic Method (USP) or
Xylene Method (US Forestry Service) or
5. Hexane
Moisture Method by Toluene Distillation (NF)
-drugs with Fats and Fatty Oils
-for vegetable drugs containing 2% of
moisture
Crude Fiber
-disadvantages: requires a comparatively
-the residue, consisting of chiefly cellulose, that
large amount of drug
remains undissolved after successive treatment
with boiling acid and alkali
3. Dew Point Method
-important for detection of adulterants
-drugs with low concentration of water
-limitations on the amount of substance that is
insoluble in a given solvent
4. Electrolytic Hygrometric Method
-checks the purity and identity of the drug
-drugs with very low concentration of water
-gravimetric method
5. Karl Fischer Electrometric Titration
Constants of Fats, Fatty oils, Waxes, Balsams, Resins,
-water equivalence factor (F) mg H2O / mL KFR
etc.
-employs the use of Na2C4H4O6 . 2 H2O as
-turbidity of the oil sample is due to the separation
primary standard or water-methanol solution of
of stearin
known concentration as secondary standard
-heating in a water bath at 50oC
-end point of titration increase current
 -method of analysis consist of the determination Koettsdorfer Number
of physical and chemical properties or values Saponification Value Limits
commonly known as constants Substance SV
-when taken in conjunction with color, odor, taste Castor oil 176 182
and special identity tests for the given substance Corn oil 187 193
and for common adulterants are the basis upon Olive oil 190 195
which the purity and quality of these substances Almond oil 190 200
Cod Liver oil 180 192
are judged
Persic oil 185 195
Acid Value (Acid Number; Acidity Index)
Ester Value (Ester Number)
-presence of free acids due to hydrolysis of esters
-number of milligrams of KOH required to
and caused by chemical treatment, by bacterial
saponify the esters in 1 g of sample
action or by the catalytic action of light and heat
-in substances that do not contain free acids, the
-number of milligrams of KOH necessary to
EV is equal to the SV
neutralize free acids in 1 g of sample
-when free acids are present, EV is the difference
-number of milliliters of 0.1 N NaOH required to
between AV and SV
neutralize free acid in 10 g of sample
-important in the analysis of yellow and white
-Direct Alkalimetric Method
wax it serves to indicate the presence of
-Data: weight of sample, N & mL of NaOH
adulterants (e.g. paraffin)
-Alkalimetric Method using Back Titration (w/
Acidity Limits: USP & NF
Substance Amount Alkali used Official Blank Test)
used (g) requirement
(mL)
Corn oil 10 0.02 N NaOH =/<2
Olive oil 10 0.1 N NaOH =/<5
Almond oil 10 0.1 N NaOH =/<5
Cod Liver oil 2 0.1 N NaOH =/<1
Tolu Balsam - - 112 168
Yellow Wax - - 18 24

Saponification Value
-number of milligrams of KOH required to
neutralize the free acids and saponify the esters
contained in 1 g sample
-serves to aid in the detection of the presence of
the glycerides of acids containing less than 16 or
more than 18 carbon atoms
-indicate adulteration with unsaponifiable matter,
such as mineral oil
-inversely proportional to the mean molecular
weights of the acids present
-Alkalimetric Method using Back Titration (w/
Blank Test)

Saponification Number
-Data: weight of sample
mL alcoholic KOH
mL HCl (BT & AT)
N KOH
M HCl