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TITRATION

QUALITY CONTROL with Drug Assay

TITRATION

titalus (Latin) inscription or title


titre (French) rank
a
common
laboratory
method
of
quantitative/chemical analysis that can be
used to determine the concentration of a
known reactant (analyte)
The basis of the method is a chemical
reaction of a standard solution (titrant)
with a solution of an analyte.
Because volume measurements play a key
role in titration, it is also known as
volumetric analysis

Usually, it is the volume of the titrant


required to react with a given quantity of an
analyte that is precisely determined during
a titration.

TITRATION

The process of adding a


measured amount of a
standard
solution
to
a
specified amount of sample
solution in order to find the
concentration of a certain
ion in the sample solution.

BASICS OF TITRATION

Essentials of Titration

Titrant

Analyte

Indicator

Setup for a Typical

Essentials of Titration

Titrant (or Standard Solution) - A


solution of known concentration used in
a titration
Analyte
(or
Titrand
or
Sample
solution) is a solution of the substance
whose concentration is unknown and
sought in the analysis
Indicator - A substance which will change
colour or do something else to show that
the titration is complete

Titrant / Standard Solutions

Standard Acid Solutions

Hydrochloric Acid
Sulfuric Acid

Standard Alkali Solutions

Sodium hydroxide
Potassium hydroxide
Barium hydroxide

Standard Acid Solutions

HCl is preferred in the titration of


compounds that yield precipitate, such
as Ba(OH)2
H2SO4 is preferred in hot titrations, since
HCl losses chlorides during volatilization

Standard Alkali Solutions

Alkali solutions absorb carbon dioxide from


the air changing rapidly in concentration
NaOH and KOH may become contaminated
with carbonates liberation of CO2 during
acid alkali titration
Ba(OH)2 solutions is free from carbonates
CO2 is pptd. as BaCO3 thus decreasing the
conc. of Ba(OH)2 in soln
Alkali solns should be restandardized
frequently

Indicators

Three (3) Theories in the


change of color of indicators:

Physicochemical Theory change in color is due to


increase or decrease in certain ions

Methyl Red, Phenolphthalein, Methyl Orange

Organic Theory the color of the indicator is due to


certain groupings of the elements in a compound and the
change in color is due to change in molecular structure

Increase in ions appearance of new color


Decrease in ions disappearance of a color or the appearance of
a different color

Eriochrome Black, Hydroxynaphthol blue, Xylenol orange,


Pyridylazonaphthol

Colloidal Theory assumes that indicators form a


colloidal solutions and change in color is dependent on
the change in size of the colloidal particle

Eosin Y, TEE, DCF

Rules in the Use of Indicator


1.
2.

3.
4.
5.

6.

Use 3 drops of indicator unless otherwise directed.


Strong acid titrated with Strong Alkali (vice versa)
Methyl Red, Methyl Orange, Phenolphthalein
Weak Acid titrated with Strong Alkali
Phenolphthalein
Weak Alkali titrated with Strong Acid Methyl Red
Weak Alkali should never be titrated with Strong
Acid, or vice versa, since no indicator will give a
sharp end point.
The appearance of a color is more easily observable
than is the disappearance always titrate where
possible to the appearance of a color

Mixed Indicators
use to sharpen up the color change
Methylene Red Methylene Blue
Xylene Cyanol Methyl Orange
Bromocresol Green Methyl Red
Bromocresol Green Chlorophenol Red
Cresol Red Thymol Blue
Thymol Blue Phenolphthalein

Equipments used:

Volumetric Apparatus

To deliver a definite volume of liquids


Burettes

/ Burets
Pipets / Pipettes

To contain a definite volume of liquids


Volumetric

flasks
Graduated cylinders

Sources of Error in the Use of


Volumetric Apparatus

Water adhering to apparatus Rinse and discard washings


Grease films and dirty apparatus cause irregularity in the delivery of
liquids and distort the meniscus rinse the apparatus prior to usage
Parallax must be a voided proper readings must be practice
always
Variations in temperature leads to change in volume of the vessels
and liquids measurements must be done at a temperature closely
approximating to that of the calibration of the vessel
Air bubbles trapped beneath the liquid surface, specially below
burets stopcock displace liquid
Heat coming from hot solutions causes change in volume let it
cool
Most salts dissolved produce a change in temperature, with
concomitant change in volume of the solution acquire the
temperature at which the apparatus is calibrated
Failure to used the apparatus properly learn more about what you
are using

Equipments used:

Volumetric Apparatus

Buret
Pipette
Buret funnel
Volumetric Flask
Erlenmeyer Flask (usually 250 mL)
Beaker,

250ml
Stirring rod

pH meter

Buret

Also burette
is a device used in analytical chemistry
for the dispensing of variable, measured
amounts of a chemical solution

Buret

Classification:

Class A

Class B

10

0.02

0.04

25

0.03

0.06

50

0.05

0.10

100

0.10

0.20

Analogue

A traditional burette consists of glass tube of constant bore with a


graduation scale etched on it and a stopcock at the bottom
The barrel of the stopcock may be made of glass or the plastic PTFE.
Stopcocks with glass barrels need to be lubricated with vaseline or a
specialized grease.
Burettes are manufactured to specified tolerances, designated as class A or
B and this also is etched on the glass
Temperature and grade are shown at the top.

Digital

Burette accuracy
/mL

Volumetric burette delivers measured volumes of liquid

Capacity,
mL

based on a syringe design


The barrel and plunger may be made of glass.
With liquids that corrode glass, including solutions of alkali the barrel and
plunger may be made of polyethylene or another resistant plastic material.
The barrel is held in a fixed position and the plunger is moved
incrementally either by turning a ratcheted wheel by hand, or by means of
a step-motor.
The volume is shown on a digital display.

Piston burettes are similar to syringes, but with precision bore


and plunger, manually operated or motorized
Weight burette delivers measured weights of liquid

Buret

is a cylindrical tube with a stopcock at one end


made to deliver definite volume of liquid
carefully calibrated piece of instrument that is
used to measure out an exact amount of solution.
Graduated in 0.1 mL increments
Types:

Acid Burette (Geissler)

Geissler Buret w/ glass stopcock with a ground glass


stopcock
Geissler Buret w/ Teflon stopcock stopcock and tip are
polymethylpentene (PMP) with leakproof, self lubricating
Teflon stopcock plug. For dilute acids and bases but avoid
alcohol and organic bases. Economy grade.

Base Burette (Mohr) with a pinchcock as its stoppers

Geissler Buret
Geissler Buret with Teflon
stopcock

Geissler Buret with Glass


stopcock

Mohr Buret

Using a Buret

Always rinse buret with water


(from a beaker, not the faucet)
first.
Second, rinse(2-3 times) with a
small amount of the titrant and
drain it through the tip.
Check if the buret is flowing
freely.
To fill a buret, close the stopcock
at the bottom and use a funnel.
You may need to lift up on the
funnel slightly, to allow the
solution to flow in freely.
Do not waste time trying to fill
the buret to zero for each
titration.

Using a Buret

You can also fill a buret


using a disposable
transfer pipet. This
works better than a
funnel for the small, 10
mL burets. Be sure the
transfer pipet is dry or
conditioned with the
titrant, so the
concentration of
solution will not be
changed.

Using a Buret

Fill the buret tip by


momentarily opening the
stopcock.
Check the tip of the buret
for an air bubble. To
remove an air bubble,
whack the side of the
buret tip while solution is
flowing. If an air bubble
is present during a
titration, volume
readings may be in error.

Using a Buret

Rinse the tip of


the buret with
water from a
wash bottle and
dry it carefully.
After a minute,
check for solution
on the tip to see if
your buret is
leaking. The tip
should be clean
and dry before
you take an initial
volume reading.

Using a Buret

When your buret is conditioned and


filled, with no air bubbles or leaks,
take an initial volume reading. A
buret reading card with a black
rectangle can help you to take a
more accurate reading. Read the
bottom of the meniscus. Be sure
your eye is at the level of
meniscus, not above or below.
Reading from an angle, rather than
straight on, results in a parallax
error. Remember that burets are
graduated in a downward direction.
The first estimated digit will
probably be the hundredths place.

Using a Buret

Deliver solution to
the titration flask
by turning the
stopcock. The
solution should be
delivered quickly
until a couple of
mL from the
endpoint.

Using a Buret

The endpoint
should be
approached
slowly, a drop
at a time. Use
a wash bottle
to rinse the
tip of the
buret and the
sides of the
flask.
Do not start
above the 0
mL mark or
titrate past
the 50 mL
mark.

Titration Notes

Always use white paper underneath your sample flask so that you
will notice slight color changes.
Learn to swirl the flask without removing it from underneath the
buret.
Use a drop, drop, drop pace until you see the color change
becoming more than local (where the titrant meets the sample).
Now proceed dropwise.
Second and third trial titrations should always be fast assuming the
sample will be about the same because you now know
approximately how much titrant is needed. If the first titration
required 25 mL than you can add 22 mL all at once and then
proceed cautiously.
Remember that the amount of water used to dilute the sample is not
crucial because it does not affect "how many" of the sample
molecules are present in the sample flask. Diluting with water allows
you to see the color change easier.
Always label multiple burets and sample flasks.
Remember to add indicator.

Pipettes / Pipets
Used to deliver or measure standard
volume of liquid
Common pipets:

Air

displacement micropipettes
Positive displacement pipette
Volumetric pipettes
Graduated pipettes
Pasteur pipette
Transfer pipettes

Volumetric pipettes

or bulb pipette allow the user to measure a volume of


solution extremely accurately (accuracy of four
significant figures).

Aka: TRANSFER or DELIVERY PIPETS

These pipettes have a large bulb with a long narrow


portion above with a single graduation mark as it is
calibrated for a single volume (like a volumetric flask).

Usually available in 1ml, 2ml, 5ml, 10ml, 25ml, 50ml,


100ml

Volumetric pipettes are commonly used to make


laboratory solutions from a base stock as well as prepare
solutions for titration

Used for accurate measurements since it is designed to


deliver only one volume

Accurate and precise measurement accurate to four


significant figures

Designed such a fluid is dispensed, a small drop of liquid


will remain in the tip DO NOT BLOW let the tip touch
the wall of the flask and give a half - twist

Specifications on Volumetric
Pipettes
The following must be indicated
How much liquid will be transferred if the
liquid is drawn up to the calibration line on
the neck
The temperature at which the calibration
was made

Graduated pipettes

Aka: MEASURING PIPET


are a type of macropipette consisting of a
long tube with a series of graduations, as
on a graduated cylinder or burette, to
indicate different calibrated volumes
Graduated pipettes are often graduated in
one of two ways:

Mohr, backward or drain-out pipettes

The graduation on these always end before the tip

Serological, forward or blow-out pipettes

The graduation marks continue to the tip

Graduated pipettes
A Mohr, backward or drain-out
pipette

Serological, forward or blow-out


pipette

Specifications on Measuring
Pipet
Printed on the neck of the pipette are the specifications
that indicate:
The maximum volume of liquid that can be transferred
The size of the divisions on the pipet
The temperature at which calibrations were made
If the pipette is a to deliver (TD) or to contain (TC)
pipette

Pasteur pipettes

are plastic or glass pipettes used to


transfer small amounts of liquids, but are
not graduated or calibrated for any
particular volume
they are also called as teat pipettes,
droppers, eye droppers and chemical
droppers

Standard method of
TITRATION

A known volume of the analyte is placed in a titration flask.


The burette is filled by a standard solution (titrant,) of
known concentration.
Before the titration is started, 1-3 drops of indicator
(phenolphthalein) is placed in the titration flask with the
analyte. The chosen indicator must be one color when the
solution is acidic.
A base solution is then slowly added from the burette, drop
by drop.
The titration continues, drop by drop, until the indicator
suddenly achieves the intermediate color (weak pink)
between that of the acid and the color of the base
(fuchsia). At that point the titration ceases.
The point at which the system is neither acidic or basic is
referred to as the endpoint. The endpoint will correspond to
a perfect stoichiometric relationship between the acid and
the base.
Once the endpoint has been reached, the burette must be
read. The bottom of the meniscus line determines the
quantity of the base that was required to reach the
endpoint.
Once the titration is completed, the final calculations can
be done.

Titrating with a pH meter

Titration with a pH meter


follows the same
procedure as a titration
with an indicator, except
that the endpoint is
detected by a rapid
change in pH, rather than
the color change of an
indicator.
Arrange the sample,
stirrer, buret, and pH
meter electrode so that
you can read the pH and
operate the buret with
ease.

Definitions:

Standard Solution a solution of known


concentration
Standardization

Primary Standard
Secondary Standard

Titer

Titrimetry

measuring the quantity of a reagent of


known concentration required to react
with a measured quantity of sample of
an unknown concentration

Titrimetry Types

Volumetric Titrimetry
Gravimetric or Weight Titrimetry
Coulometric Titrimetry

Titrimetry Types

Volumetric Titrimetry - involves measuring the


volume of a solution of known concentration that
is needed to react completely with the analyte.
Gravimetric or Weight Titrimetry - differ only
in that the mass of the reagent is measured
instead of its volume.
Coulometric Titrimetry - The reagent is a
constant direct electrical current of known
magnitude that consumes the analyte, the time
required and thus the total charge to complete
the electrochemical reaction is measured.

Titration Reaction types

Acid-Base Titrations
Titration Reaction types

Acid-Base Titrations

a process of neutralization whereby a titrant (a solution


of known concentration) is delivered into an analyte
(unknown solution) until the unknown solution is
completely neutralized
An indicator is (often) a weak acid that is placed into
the unknown solution to determine the endpoint of the
titration (the pH at which the indicator changes color)
The equivalence point of the titration is the point when
the moles of H+ are equal to the moles of OH- in a
titration
The progress of an acid-base titration is often
monitored by plotting the pH of the solution being
analyzed as a function of the amount of titrant added.
The graph produced is called a Titration Curve.

Types of acid-base
Titrations

Strong Acid / Strong Base

Weak Acid / Strong Base

pH at equivalence point = 7
pH at equivalence point >7

Strong Acid / Weak Base

pH at equivalence point <7

Note: weak acid / weak base titrations are too


complicated and are almost never carried out.

Indicators of Acid Base


Reactions

Applications of acid-base
titration

In the determination of iron in


pharmaceutical preparations
First of all, acid-base titration, to control
acidity or alkalinity of solutions, to do
neutralization tests and analyze
mixtures of acids
Wide use is in titration processes

RedOx Titrations
Titration Reaction types

RedOx Titration

Titration of a reducing agent by an


oxidizing agent or titration of an
oxidizing agent by a reducing agent. The
concentrations of redox-active species
can be determined by redox titrations.
In a redox titration, a measured sample
of the unknown is titrated against a
standard solution of a substance that will
oxidize or reduce the unknown.