Principles of Volumetric Analysis

Primary Standards apuresubstances to prepare standardsolutions

amount in moles can be calculatedaccurately from
theirmass and are called primary standards
readily be obtainable in a pure form
known chemical formula
easily stored withoutreacting1deteriorating
Amolar mass to minimise elketof errorsin weighin
be cheap

Example
bases Anhydrous sodium carbonate CNaaCO

and sodium borate

Na BaO IO H2O

Acids hydrated oualic acid Hac 04 Ha0 and

potassium hydrogen phthalate KH CCg Hc 04
Standard solutions prepared by dissolving an accurately
measured mass of a primary standard
in water to make an accurately measured
volume of solution
or
prepared by performing a titration with
another standard solution in order to
determine its enact condition

The Molar concentration of the standard solution can then

be found from the following formulas

Amount in moles n mass of solute cgs

molarmasscgmoi t My

concentration C amount of solute Cin ma n

volume of solution T v
Conducting Volumetric Analysis undertaking a titration

Dilution Many standard solutions such as sodium hydroxide

are prepared as relatively high concentration stock solutions

To obtain a convenient concentration to use in titration these

stock solutions should be diluted

Titration Volumetric analysis involves reaching a measured

volume of a standard solution with a measured volume
of the solution of unknown concentration
These solutions are mined until they have just reacted
completely in the mole ratio indicated by the balanced
chemical equation equivalence
point Is this process is
known as Titration
Steps involved in an acid base titration

1 A known volume of one of thesolutions is measured

using a
pipette and transferred into a conical flask The
fined volume of solution transferred by a pipette is called
an aliquot

2 A few drops of an appropriate acid base indicator are added

sothat colour change signals the point at which to tratron
should shop

3 The other solution is dispensed slowly into the conical flash

from a burette until the indicator changes colourpermanently
 The volume of the solution delivered by a burette is
called a titre which is calculated by subtracting initial
burette reading from the final burette reading

To
moths
minimise errors the titration is repeated several times
and the average film is found Usually 3
Concordant litres titres which are within 0.10mL fromthe
highest to lowest of each other are used to find the
average

Selecting an Indicator
During a volumetric analysis the pH of thesolution in the
conical flash changes as liquid is delivered from the burette

This is graphically represented in a TitrationCurve1pH came

The equivalencepoint the point in the titration where

is
the two chemicals have reacted in the mole ratio
indicated by the balanced chemical equation as seen below

gradientofthe
curve is steepest
 The point in titration when the indicator changes colour
is known as the end point It is important to select
an indicator that changes colour during the steep section
of the pH change so that the end point and the
equivalence point occur at the same time during the
titration

The colours of common acid

base indicators and thepH
range over which they colour change are

RinsingVolumetric Glassware
Acid base titrations of organic compounds

Organic Acids and Bases

Organic acids are common in everyday materials

Organic bases are less common

carbonyl functional Group

Carbouylic acids are most common organic acids
carhorylic acid functional group C COOH
Its a weak acid as they can partrally donate a
hydrogen ion Ht

Most organic acids that contain a carbonyl group

are Monopheelic Acids meaning they can only donate 1

proton
Example
CHzCOOHcags t NaOHcag CH COONa cap H2O

Some organic acids are polyproclic acids and can

donate more than A proton
Example
CaHa04cap th NaOH cap NaGQ cast 2420cg
Amino Functional Group
Organic bases typically contain a Nitrogenatom in the
molecule which can accept a hydrogen ion

Amines are a common Caminemoleculecontains

organic base
an amino functional group C NHI

Amines can actlike bases and acceptprotons due to the

lone pair of electrons on the nitrogen atoms

Amines react with acids to produce salts

Example
CaHsNHA capt HCl cap CatsNHz Clean
ethanamine hydrochloricacid ethylammoniumchloride
 Analysing Organic Acids and Bases
Carbouyheawds are weak acids
Amines are weak bases

iff The volumetricanalysis of organicacids and bases is performed

using story acids and bases to ensure near complete reaction

sharper colour change in the indicator with a more
precise end point

Example Question

Cath04cag theNaOHcap Nazca04cag t 2h20 a

Average titre 22.10 223.02
22.06 22.06mL

h CNaOH C XV l X 0.02206 0.02206 not

i n CaHaq n NaOH 2 0.01103
o HzOa
 Example Question

HzCHANHaccept HCl cag CHzCHANHzClcaop

Averagetitre 21.482
21.501
213401 21 46mL

hCHCH 0.100 0.02146 0.002146Mol

CXV
NCH hCCHzCHANHa 0.002146m01
ooo CC
CHzCHzNHz na 0.002146 0.02 0 107M

Redon titrations of organic compounds

Analysing Organic compounds by Redou titrations

A redou titration involves the reaction of an ouidising agent
with a reducing agent whereas acidbase titratrons have
one solution pipelted into a conical flash and the other
is dispensed into the flash from a burette

Theequivalence can be measured 2 ways with redou

point in

titrations colour change or adding an indicator

 With volumetric analyses using redou titrations we
can identify the composition of a range oh substances

Analysing Alcohols Alcohols can

undergo oxidation and act
as Weak Reducing Agents

When a
primary alcohol ethanol is onidised the hydrougl
functional into an Aldehyde group C CHO
group is converted
This can be further ouidised to a carbonyl functional group
C COOH as shown below

These ouidation reactions can be used as the basis for

volumetric analysis to determine the concentration of an
alcohol in a solution

Typically a strong ouidising ouidising agent such as

acidified potassium dichromate solution CK2CraQ or
acidified potassium permanganate solution CKMn04 is
 e e a 0
Example Question

Average titre 14.13 141181 14,11 14.14mL 0.01414L

3

h KMnOy Cxv 0.125 0.01414 0.0017675moi

n Chun 4 XS n C CH OH 0.002209mole CCCHzOH5 0.221M
4

Selecting indicators for Redon titrations

Its difficult to select suitable indicators for
redou titrations than her acid base titrations Redon
indicators must behave as ouidants or reductants after
the equivalence point has been reached and a small
eucess of solution fromthe burette is present They must
also be highly coloured in either ouidised or reduced
form

The permanganate icon is used often in redou titrations

The permanganate icon is purple white manganese CIIions
 MnOg cap tf H tcap Se Mnhteagst4thOct
purple colourless

i No need to use a redou indicator in titrationsusing the

ion permanganate
But starch is used as an indicator in titrations in
which Iodine Iz is either a reactant or product When
Iodine is present in encess it reacts with starch to form a
Dark blue complete as seen below t