TITRATION INVOLVING (PERMANGANOMETRY)

AQUEOUS

POTASSIUM

PERMANGANATE

Potassium permanganate is a powerful oxidizing agent in the presence of an acid .In acidic medium it oxidizes oxalic acid to carbondioxide; metal oxalate to metal salt and carbondioxide , ferrous salts to ferric salts and so on. In acid solution the reaction can be represented by the following equation: Mn
"

$%#

& e"

Mn'#

!%'

(ulphuric acid is the most suitable acid .)ith %*l the reaction 'Mn
! "

# +,*l" # +-%#

'Mn'#

# &*l'

# $%'

may ta.e place and some permanganate may be consumed in the formation of chlorine /side reaction0. 1herefore, %*l should not be used to acidify 2Mn ! It is difficult to obtain potassium permanganate perfectly pure and completely free from manganese dioxide /Mn '0. Moreo3er, ordinary distilled water is li.ely to contain reducing substances /traces of organic matter etc.0 which will react with the potassium permanganate to form Mn ', which in turn, catalyses the auto decomposition of the permanganate solution on standing. 4ue to these reasons potassium permanganate solution is not primary standard, that is, 2Mn ! solution of desired concentration can not be prepared simply by dissol3ing calculated amount of potassium permanganate crystals. 1herefore, potassium permanganate solution is standardized 5ust before it is used to titrate other solutions. Potassium permanganate solution may be standardized using standard sodium oxalate or oxalic acid. In acidic medium, oxalic acid reduces Mn ! gi3ing colourless solution. Mn
! "

$%# /*

# &e" %0' # &/* %0'

Mn'# '*
'

# !%' # '%# #'e" 'Mn'# # +,*

6' 6 & # $%'

'Mn

"

# -%#

'

' moles of 2Mn ! & moles of /* %0' 7o external indicator is used as the colour of 2Mn ! acts as the indicator. In a flas. fixed 3olume of oxalic acid /standard0 is mixed with dil % '( !.)arm solution /-,"8,*0 of this mixture is titrated with 2Mn ! solution .9efore end point pin. colour of 2Mn ! disappears but at the end point faint pin. colour persists for :, seconds. 9y this method the concentration of potassium permanganate solution is determined. 7ow the standard solution of 2Mn ! can be used to titrate other reducing agents li.e iron /II0 ion, hydrogen peroxide.

EXPERIMENT: TO ESTIMATE THE AMOUNT OF IRON IN A GIVEN SAMPLE OF MOHR'S SALT BY TITRATING IT WITH STANDARD POTASSIUM PERMANGANATE SOLUTION. APPARATUS: 9urette, pipette, *onical flas., ;olumetric flas. /'&,cm:0 ,)atch glass . THEORY: Potassium permanganate is a powerful oxidizing agent in the presence of an acid .In acidic medium it oxidizes oxalic acid to carbondioxide ,metal oxalate to metal salt and carbondioxide ,ferrous salts to ferric salts and so on .In acid solution the solution can be represented by the following equation. Mn
! "

$%#

# &e"

Mn'# #

!%'

4ilute sulphuric acid is the most suitable acid for this purpose. 4ilute %*l should not be used because with %*l the reaction 'Mn !" # +,*l " # +-% # 'Mn'# # &*l ' # $%' may ta.e place and some permanganate may be used in the formation of chlorine.

Mohr<s salt /ferrous ammonium sulphate0 is a double salt of the formula =e( !. /7%!0'( !. -%' .=errrous ammonium sulphate is the most 3aluable of the ferrous salts for 3olumetric wor. because it does not oxidize in air rapidly as ferrous sulphate does, and it can be obtained in a state of approximating closely to perfect purity. )hen dissol3ed in water the double salt brea.s up into simple salts, i.e ferrous sulphate and ammonium sulphate. nly the former /ferrous sulphate0 reacts with the permanganate. =e(
! .

/7%!0' (
!

-%' # +, =e(
!

=e( &=e' /(

# /7%!0' (
! :

#-%'
!

'2Mn or,

# $%'(
"

0 # 2'(

# 'Mn(

# $%'

&=e' # # Mn i.e.,

# $% #
! "

&=e:# # Mn'# # !%' & moles of =e' #

+ mole of Mn

7o external indicator is used in this titration. 9efore end point colour of permanganate disappears. >t the end point last drop of permanganate produces permanent faint pin. colour. =rom the number of moles of Mn !" ions used in the titration, the number of moles of iron /and the amount of iron also0 present in the gi3en amount of Mohr<s salt can be determined. /relati3e atomic mass of =e?&&.$!0 PROCEDURE: +. )eigh out accurately about @.$'g. >.A.quality Mohr<s salt on a watch glass. 1ransfer the weighted sample in a '&,cm: measuring flas. with the help of air"free distilled water /cold0 .>dd more air free water to fill half of the bulb.

/(ince distilled water contains certain amount of dissol3ed air and this may oxidize the ferrous ion to ferric ion the solution will ha3e to be made in air free water. (o before starting this experiment air free water should be first prepared. 1o prepare air free water boil distilled water bris.ly for about +& minutes in a flas. fitted with a 9unsen 3al3e0. '. 1hen add 3ery slowly about +,cm : cone. (ulphuric acid. (ulphuric acid pre3ents oxidation of ferrous ion by atmospheric oxygen. (ha.e well to dissol3e the solid. >llow the flas. to cool down to room temperature. 7ow ma.e up to '&, cm: with air free water. (ha.e well. :. Ainse the pipette with Mohr<s salt solution and then pipette out +,cm : of the solution and transfer it into a conical flas.. >dd about +,cm : bench sulphuric acid again. Aun the permanganate solution from the burette until a faint pin. colour persists .4uring titration conical flas. should be constantly swirled. /Bnli.e oxalic acid or oxalates, the oxidations of ferrous solutions proceeds in cold. %ence solution of ferrous salts are titrated against potassium permanganate solutions in cold otherwise oxidation of ferrous ion by atmospheric oxygen may occur0. !. Aepeat procedure no. : to obtain at least two concurrent readings: OBSERVATION: 7o. *oncentration of potassium permanganate solution ? final 9urette reading difference concurrent reading

;olume of Mohr<s salt solution ta.en initial

1itration summary: +,cm: of Mohr<s salt solution consumedCCCCCCC cm : of supplied potassium permanganate solution. RESULT: >mount of iron in CCCCCCCCCC g of Mohr<s salt is CCCCCCCCCC g . Percentage >mount of iron /by weight0 is CCCCCCCCCCCCCCCCC SPACE FOR CALCULATION: