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Just an idea on how to start this. thank you Experiment 6

Titrations with KMnO4 

 

Introduction:

Potassium permanganate is a strong oxidizing agent as indicated by its large positive standard reduction potential value of 1.507 volts in acid medium.

MnO4−  +    8 H+   + 5e- ⎯→ Mn2+   +4 H2O E°  =  1.507 V

 

In titrimetric analysis, it is frequently used as titrant due to its intense coloring power, which requires no auxiliary indicator.  When the titration is carried out in acidic medium, the permanganate ion is reduced to the colorless manganous ion (Mn2+) in aqueous solution.  A drop of excess permanganate turns the solution into pink color, which could last for about 15 seconds. This color is taken as the endpoint of the titration.  The solution must be kept inside a brown bottle because it readily decomposes to brown MnO2 upon reaction with sunlight.  

 

Direct titration with KMnO4 is an analytical procedure commonly used by analysts because it does not require the use of an auxiliary indicator.  Samples that contain Fe2+ react quantitatively with KMnO4 in cold, acid solution but reaction with oxalate ion occurs quantitatively in hot, acid solution.  A commercial sample of hydrogen peroxide can also be analyzed by direct titration where the H2O2 present in the sample is oxidized to O2.   Commercial samples of hydrogen peroxide are encountered as aqueous solutions of containing about 6%-30% (w/v) H2O2.  A more common way of expressing the composition of these commercial products is by indicating the volume of oxygen liberated when the solution undergoes decomposition by boiling according to the equation written below:  :

 

2H2O2(aq)   ⎯⎯→  2H2O(l)  +  O2(g)

 

Thus 1 mL of a sample of hydrogen peroxide with the label 20-volume will yield 20 mL of O2 measured at standard temperature and pressure (STP).  The label 20-volume refers to a 6% (w/v) H2O2, 40-volume is also 12% (w/v) H2O2, and 100-volume hydrogen peroxide refers to 30% (w/v) H2O2.  For the procedure described below, the suitable samples to use labeled as 10-volume or 20-volume H2O2.



Experimental Procedure

  • Preparation of a 0.02 M Potassium Permanganate.

Weigh approximately 1.6-g of a good grade potassium permanganate and place it in a 250-mL beaker. Dissolve the salt by adding 50-mL of water and stirring. Decant the solution into a large beaker and add 50-mLof additional water to dissolve the crystals remaining in the first beaker. Repeat this procedure until all crystals are dissolved. Dilute the solution to about 0.5 L, transfer to a glass-stoppered bottle and label properly.

 

Note: Consult the lab instructor if the treatment procedure described below is necessary.  

To remove MnO2 proceed as follows: Before transferring the solution to the bottle, heat it just to boiling and keep it slightly below the boiling point for 1 hour. Allow the solution to cool, filter it through a sintered glass crucible using suction and transfer the solution to a glass-stoppered bottle.  

 

  • Standardization of Potassium Permanganate Solution (McBride Method)

Accurately weigh three samples of about 0.20 to 0.25-g each of dried sodium oxalate into clean 250-mL Erlenmeyer flask.  Dissolve each sample in about 75-mLof 0.75 M H2SO4.  Then heat the first solution to almost boiling point (80 to 90oC) and titrate slowly with the permanganate through constant swirling.  The endpoint is marked by the appearance of a faint pink color that persists for 30 seconds.  The temperature should not drop below 60oC during titration.  Titrate the two other solutions in the same manner.

Add permanganate solution dropwise to about 100-ml of 0.75M H2SO4 until the color matches that of the titrated solution. This volume should be subtracted from the volume used in the titration.

 

Report the molarity of the permanganate solution.

 

Note:  

  1. Aqueous solutions of 0.75 M H2SO4 can be prepared by mixing 20 mL of concentrated H2SO4 in 400 mL distilled water.  
  2. Rapid titration can lead to the formation of a brown precipitate, MnO2.  The persistent appearance of the brown color precipitate will introduce error to the standardization.  
  3. Maintain the temperature range required for the reaction.



  • Preparation of the Impure Sample Containing Ferrous Ammonium Sulfate 

Each group will be given an unknown based on your Group No.  Weigh each of the unknown samples by difference and transfer each one into a dry flask.  Record the mass (g) of the unknown obtained for each trial.  Dissolve the unknown in 75 mL of 0.75M H2SO4 and titrate with the permanganate solution with constant swirling until the appearance of a faint pink color for about 30 sec.  

Repeat the same procedure with the other 2 samples.  

 

Report the composition of your sample in terms of % Fe(NH4)2(SO4)2·6H2O

 

  • Determination of Hydrogen Peroxide 

 

For this experiment a 10-volume H2O2 sample is an appropriate to use.  

 

Transfer a 25 mL aliquot of the sample to a 500 mL volumetric flask and dilute to the mark.  Label this as dilute sample solution.  Measure a 25 mL aliquot portion of the dilute sample solution and transfer into an Erlenmeyer flask.  Add 20 mL of distilled water, 20 mL of dilute H2SO4 solution (1:5 dilution) and titrate with 0.02 M KMnO4 to the first permanent faint pink color.  Repeat the titration to two consecutive determinations and the trials should agree within 0.1 mL. 

 

Express the concentration of the sample in terms of %(w/v) H2O2.  








 Experiment 6:  Data & Calculations 

Titrations with KMnO4 

 

Table 1.  Standardization of 0.02 M KMnO4 Against the Primary Standard Sodium Oxalate

Balanced Chemical Equation:



Details

Trial 1

Trial 2

Trial 3

Mass (g) of container plus Na2C2O4

-

-

-

Mass (g) container less Na2C2O4

-

-

-

Mass (g) Na2C2O4

0.2278

0.2014

0.2070

Amount (mmoles) Na2C2O4

     

Amount (mmoles) KMnO4 reacted with Na2C2O4

     

Final Buret Reading

-

-

-

Initial Buret reading

-

-

-

Volume (mL) of the KMnO4 Solution Delivered

34.10

30.10

30.70

Molarity of KMnO4 Solution

     

Average Molarity of KMnO4 Solution

 

Deviation

 

 

 

Standard Deviation

 

Coefficient of Variation (%RSD)

 




Table 2.  Analysis of an Impure Sample of Ferrous Ammonium Sulfate Hexahydrate

Balanced Chemical Equation:

Details

Trial 1

Trial 2

Trial 3

Mass (g) of packet plus sample

-

-

-

Mass (g) of packet less sample

-

-

-

Mass (g) sample

1.0320

1.1038

0.9750

Average Molarity of KMnO4 solution

 

Final Buret Reading

-

-

-

Initial Buret reading

-

-

-

Volume (mL) of the KMnO4 Solution Delivered

18.33

19.60

17.33

Amount (mmoles) KMnO4 needed to reach the end point

     

Amount (mmoles) Fe2+ reacted with KMnO4

     

Amount (mmoles) Fe(NH4)2(SO4)2⋅6H2O 

     

Mass (g) Fe(NH4)2(SO4)2⋅6H2O  present in the sample

     

Mass Percent Fe(NH4)2(SO4)2⋅6H2O,

%Fe(NH4)2(SO4)2⋅6H2O

     

Average %Fe(NH4)2(SO4)2⋅6H2O

 

Deviation

 

 

 

Standard Deviation

 

Coefficient of Variation (%RSD)

 

Table 3.  Determination of H2O2 in a Commercial Sample

Balanced Chemical Equation:

Details

Trial 1

Trial 2

Trial 3

A.  Preparation of the Dilute Sample Solution

Volume (mL) of Liquid Commercial Sample

25.00

Volume (mL) of Dilute Sample Solution

500.00

B.  Titrimetric Analysis of the Sample Solution

Volume (mL) of DSS Titrated

25.00

25.00

25.00

Average Molarity of KMnO4 solution

 

Final Buret Reading

-

-

-

Initial Buret reading

-

-

-

Volume (mL) of the KMnO4 Solution Delivered

23.60

23.50

23.40

Amount (mmoles) KMnO4 needed to reach the end point

     

Amount (mmoles) H2O2 present in the aliquot portion of DSS

     

Total Amount (mmoles) H2O2 dissolved in the entire DSS

     

Total Mass (g) H2O2 dissolved in the entire DSS

     

% (w/v) H2O2 in the Commercial Sample

     

Average %(w/v) H2O2

     

Deviation

     

Standard Deviation

 

Coefficient of Variation (%RSD)

 

 

Answer:The titration of potassium permanganate (KMnO4) against oxalic acid (C2...

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