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Common laboratory glassware and

Dilution of solutions

Section 1

1st Common Laboratory Glassware

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How to use laboratory tools?

Upper layer

Lower layer

How to use laboratory tools?

A) Burette:
1. It is Non Volumetric glassware.
2. Wash the burette with water then with Titrant.
3. Fill the burette with Titrant up to zero.
4. In colorless solution: Upper
Adjust titrant in the burette at lower layer while layer
the colored solution, take the reading at the upper layer.
5. Put the burette at 45 angles to make sure all the air
bubbles are gone. Lower
layer

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Pipette
1. It is Non Volumetric glassware.
2. Wash the pipette with water then with Titrand.
3. Adjust colorless solution at the lower layer but the colored
solution at the upper layer.
{Because it is very difficult to determine lower layer in colored
solution}
4. Hold the pipette by the index finger.
Q: Why does the pipette give graduated volume but does not contain
this volume?
Because it contains more than 10 mL as it has a small amount of solution at
its end.

Conical flask
1. Used for washing tools and in titrations.

2. It is Non Volumetric glassware.

3. Used for preparing approximate solutions.

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Beaker
1. It is Non Volumetric glassware.

2. Used for taking approximate volumes.

3. Used for preparing approximate solutions.

Volumetric (Measuring) flask

1. It is Volumetric glassware.

2. Used for preparing standard solutions.

3. Used for diluting concentrated solution into

exactly known volume.
Q: Why does the volumetric flask contain its
graduated volume but does not give it?
Due to the attachment of some drops of the solution inside
the inner wall of the flask so it gives less volume than the
graduated volume.

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Cylinder
1. It is non-Volumetric glassware.

2. Used for taking approximate volumes

of solutions.

Glass watch
It is used to take any weight from any
chemical substance on the balancer.

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Important definitions attached to titration process

Titration:
Analytical method in which a standard solution is used to determine the
concentration of an unknown solution.
Indicator (in acid base reactions):
A weak acid or a weak base.
Indicator range:
Number of pH degrees which the color of indicator changes in.

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Equivalent point:
A point in which milliequivalent of titrant equals milliequivalent of titrand.

End point:
A point in which the color of the indicator changes in, and the titration is finished.

Titrant:
Known concentration substance in burette.

Titrand:
Unknown concentration substance in flask.

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2nd Making a dilute solution from concentrated solution

PRACTICAL

16

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If you have a concentrated HCl (C = 36%, ρ = 1.18 g/cm3 )

1. How can you prepare 250 mL of HCl 0.1N

2. Determine the normality of HCl by using NaOH (0.1210 N)

Preparation of 250 mL HCl (0.1N)



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Dilution Steps:

1. Fill ¾ volume of an empty bottle with water

2. Add 2.2 mL of concentrated HCl

3. Complete with water until 250 mL

4. Shake well

DETERMINATION OF THE NORMALITY OF HCl BY USING NaOH 0.1210 N

NaOH (B) 10 mL of diluted HCl (A)

(0.1210N) Then 2 drops of phth indicator
Titration from colorless to pink

flask

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CALCULATIONS


22

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Standard solutions
Section 2

Standard solution Non-standard solution

Is a solution that has known concentration Is a solution that has unknown concentration
exactly for fourth decimal number. and their concentration is approximated.

It is prepared in a volumetric flask. It is prepared in a 250 mL flask

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Standard Materials Non-standard Materials

1. They are pure. 1. They contain impurities.
2. They are stable. 2. They absorb moisture.
3. They are soluble in water. 3. They can react with CO2 in the air.
EX.: EX.:
Na2CO3 NaOH
K2Cr2O7 HCl
Oxalic acid { C2H2O4 } H2SO4

Preparations of standard solutions by 2 methods:

Direct method Indirect method

It is used for standard materials It is used for Non-standard materials at
at which a known weight of which an approximately concentration of
standard material is dissolved in Non-standard material is prepared and
a known volume in a volumetric this solution is adjusted by using standard
flask. solution.

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What are the precautions required for preparation of standard

solutions?
1. 99% in purity.
2. Cheap.
3. Stable chemical structure.
4. High equivalent weight.
5. Completely dissolved in water.
6. Normal conc. for solutions should be approximately equal. (For less
errors )
7. Diluting standard materials using volumetric flask while non-standard
materials using conical flask.

PRACTICAL

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You have HCl 0.1N in bottle (A), NaOH 0.1N in bottle (B), empty
volumetric flask, empty beaker, watch glass and Na2CO3 in solid state.

Requirements:

1. Prepare standard solution from Na2CO3

2. Determine Normality of HCl

3. Calculate number of grams of NaOH that found in 1 liter of solution

1- Preparation of 250 mL of a standard solution from Na2CO3:



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2- Determination of the accurate normality of HCl by using a standard solution of

Na2CO3

HCl
??? N

1. 10 mL of Na2CO3 from the

volumetric flask
2. Then 1 drop of Me.O indicator
3. Titration from yellow to orange

flask

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3- Calculation of No. of grams of NaOH in one liter solution

A- Determination of the accurate normality of NaOH by using the determined HCl in the previous
step through titration

NaOH
??? N

1. 10 mL of HCl
2. Then 2 drops of Ph.th
indicator
3. Titration from colorless to
pink
flask

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B- Calculating No. of grams of NaOH in one liter solution

Applications of using Double-Indicators

“Carbonate mixtures” {Alkaline mixtures}

Section 3

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Remember the followings

before our new section

Phenolphthalein range (8.1 – 9.9)

1.Acidic medium (colorless)

2.Basic medium (Red)
3. Neutral (Pink)

Methyl orange range (3.1 – 4.4)

1.Acidic medium (Red)

2.Basic medium (Yellow)
3. Neutral (Orange)

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The suitable indicator for titration of different acids and bases

The change in pH
Titration Suitable
degree Reason
indicator
Acid Base Before Equivalent point After

Because the change in

Strong Strong
HCl NaOH 4 7 10 Phth & M.O indicator color is sudden near
the equivalent point

Strong Weak
HCl NH4OH 4 5.1 6.2 M.O
Because the indicator range
equals the pH of salt formed
Weak Strong near the eq. point
CH3COOH NaOH 7.7 8.8 10 phth

Weak Weak Because the change in color is

CH3COOH NH4OH 6.9 7 7.1 No
gradually

Alkaline mixture

A solution that contains one or more alkaline

compound
Na2CO3 + NaOH

Na2CO3 + NaHCO3

NaOH
Na2CO3
NaHCO3

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Titration of Na2CO3 with HCl

pH Phth. M.O.
Na2CO3
12
HCl

NaHCO3 9

HCl
4
H2CO3

CARBONATE MIXTURES

PRACTICAL

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You have 5 alkaline solutions (may be mixture of solutions) with

approximately 0.1 N, and HCl in bottle (A) with 0.0901 N .
Requirements:

1. Specify the type of the solution.

2. Calculate number of grams of alkaline solution that found in 100 mL from it.

21

Unknown
Titrant
HCl St. sol.
5 carbonate mixtures
1. NaOH

2. Na2CO3
Titrand
3. NaHCO3 10 mL mixture

4. {NaOH + Na2CO3 }

5. {NaHCO3 + Na2CO3}

HCl Standard solution 0.0901 N

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Calculation of Equivalent weight Valency of Acid

Number of H+ donated
Equivalent weight {EW} = Molecular weight
Valency

Eq.w of NaOH = { (23 × 1) + (16 × 1) + (1 × 1) } = 40 Valency of Base

1 Number of H+ accepted

Eq.w of Na2CO3 = { (23 × 2) + (12 × 1) + ( 16 × 3) } = 53

2
Valency of salt
Eq.w of NaHCO3 = { (23 × 1) + (1 × 1) + (12 × 1) + ( 16 × 3) } = 84 Cations OR Anions
1

TITRATIONS
FOLLOWED BY
CALCULATIONS

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• The reading is
HCl taken at pink,
then.
• Add from the
The color turns
burette till
orange immediately
colorless
or after a few drops
• Add a drop of
of the burette, so
methyl orange.
the reading is
considered zero.
Titration

10 mL NaOH+ 2 d. Phth

Mixture Ph.th M.O Readin Indicated reading Calculations

g

HCl NaOH
Ph.th reading :
N × V = Wg × 1000
All mEq of NaOH Ew

(1) NaOH + Zero Wg = N × V × Eq.wt

1000

=……………. g/10mL

V is the burette
reading with ph.th

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• The reading is
HCl taken at pink,
then.
• Add from the
burette till
colorless Methyl orange gives
• Add a drop of a yellow color and
methyl orange. we continue the
titration until
orange.
Titration

10 mL Na2CO3+ 2 d. Phth

Mixture Ph.th M.O Readin Indicated reading

g HCl Na2CO3

N×V = ½ Wg × 1000
Ew

2 ( N × V)= Wg × 1000
Ph.th reading : Ew
½ mEq of Na2CO3
(2) Na2CO3 + + Wg = 2 × N × V × Ew
1000
M.O reading :
second ½ mEq of =……………. g/10mL
Na2CO3.
V is the burette
reading with ph.th
or M.O

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Phenolphthalein gives
a pink color before the
HCl start of the titration or
after adding a few
drops from the
burette, so the
reading is considered
zero.
We change the color
to colorless and then
add a drop of methyl
Titration orange to give a
Titrate till orange
yellow color.

10 mL NaHCO3+ 2
Phth

Mixture Ph.th M.O Reading Indicated reading

HCl NaHCO3
M.O reading :
N× V = Wg × 1000
(3) NaHCO3 Zero +
All mEq. of NaHCO3 Ew

Wg = N × V × Ew
1000

=……………. g/10mL

V is the burette
reading with M.O

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• The reading is
HCl taken at pink,
then.
• Add from the
burette till Methyl orange gives
colorless a yellow color and
• Add a drop of we continue the
methyl orange. titration until
orange.
Titration

10 mL (NaOH + Na2CO3)+ 2 d. Phth

Mixture Ph.th M.O Reading Indicated reading According to NaOH

HCl NaOH
N × V = Wg × 1000
Ew
Ph.th reading :
Wg = N × V × Ew = ….. g/10mL
1000
(4) NaOH All mEq. NaOH
V = V { ph.th} - V { M.O}
+ +
Na2CO3 ++ +
½ mEq. Na2CO3
According to Na2CO3

HCl Na2CO3
M.O reading : N ×V=½ Wg × 1000
Ew

½ mEq. Na2CO3 Wg = 2 × N × V × Ew = ….. g/10mL

1000

V is the burette reading with M.O

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• The reading is
HCl taken at pink,
then.
• Add from the
burette till Methyl orange gives
colorless a yellow color and
• Add a drop of we continue the
methyl orange. titration until
orange.
Titration

10 mL (Na2CO3 + NaHCO3)+ 2 d. Phth

Mixture Ph.th M.O Reading Indicated reading According to Na2CO3

HCl Na2CO3
N × V = ½ Wg × 1000
Ew
Ph.th reading :
Wg = 2 × N × V × Ew = ….. g/10mL
1000
(5) Na2CO3 + ++
V is the burette reading with Ph.th
½ mEq. Na2CO3
+
According to NaHCO3
NaHCO3
M.O reading : HCl NaHCO3
N ×V= Wg × 1000
Ew
All mEq. NaHCO3
Wg = N × V × Ew = ….. g/10mL
+ 1000
½ mEq. Na2CO3 V = V { M.O} - V { ph.th}

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35

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Applications of using Double-Indicators

“Phosphate Mixtures”

Section 4

TYPES OF PHOSPHATE MIXTURES

pH
Phth. M.O.
12 Na3PO4

HCl Alkaline phosphate mixtures

9 Na2HPO4

HCl

4 NaH2PO4

HCl
Acidic phosphate mixtures

2 H3PO4

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Phosphate mixtures

Acidic Alkaline

H3PO4 Na3PO4
NaH2PO4 Na2HPO4

Determined by Titration Determined by Titration

with standard alkaline with standard acidic
(NaOH) solution (HCl) solution
Double indicator method Double indicator method

PRACTICAL

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You have 3 Phosphate solutions (may be mixture of solutions) with

approximately 0.1 N, and HCl in bottle (A) with 0.0901 N .
Requirements:

1. Specify the type of the solution.

2. Calculate number of grams of alkaline solution that found in 100 mL from it.

Unknown
Titrant
HCl St. sol.
3 Phosphate mixtures

1.Na3PO4 (Tri)

2.Na2HPO4 (Di) Titrand

10 mL mixture

3.Na3PO4 + Na2HPO4 (Tri + Di)

HCl Standard solution 0.0901 N

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Calculation of Equivalent weight

Valency of Acid
Equivalent weight {EW} = Molecular weight Number of H+ donated
Valency
Valency of Base
Number of H+ accepted
EW of Na3PO4 = { (23x3) + (31x1) + ( 16x4) } = 54.7
Valency of salt
3 Number of Cations OR
Anions
EW of Na2HPO4 = { (23x2) + (1x1) +(31x1) + ( 16x4) } = 71
2

TITRATIONS
FOLLOWED BY
CALCULATIONS
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• The reading is
HCl taken at pink,
then.
• Add from the
burette till
colorless Methyl orange gives
• Add a drop of a yellow color and
methyl orange. we continue the
titration until
Titration orange.

10 mL Na3PO4 + 2 d. Phth

Mixture Ph.th M.O Reading Indicated reading

HCl Na3PO4

N×V = 1/3 Wg × 1000

Ew

3 ( N × V)= Wg × 1000
Ph.th reading : Ew
1/3 mEq. Na3PO4
+ + Wg = 3× N × V × Ew
(1) Na3PO4 M.O reading : 1000
1/3 mEq. Na3PO4
=……………. g/10mL

V is the burette
reading with ph.th
or M.O

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Phenolphthalein gives
a pink color before the
start of the titration or
HCl after adding a few
drops from the
burette, so the
reading is considered
zero.
We change the color
to colorless and then
add a drop of methyl Titrate from yellow
orange to give a till orange
Titration yellow color.

10 mL Na2HPO4 + 2 d. Phth

Mixture Ph.th M.O Reading Indicated reading

HCl Na2HPO4
M.O reading :
N× V = 1/2 Wg × 1000
(2) Na2HPO4 Zero + Ew
1/2 mEq. Na2HPO4
Wg = 2 × N × V × Ew
1000

=……………. g/10mL

V is the burette
reading with M.O

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• The reading is
HCl taken at pink,
then.
• Add from the
burette till Methyl orange gives
colorless a yellow color and
• Add a drop of we continue the
methyl orange. titration until
orange.
Titration

10 mL (Na3PO4 + Na2HPO4)
+ 2 d. Phth

Mixture Ph.th M.O Reading Indicated reading According to Na3PO4

HCl Na3PO4
N × V = 1/3 Wg × 1000
Ew
Ph.th reading :
Wg = 3 × N × V × Ew = ….. g/10mL
1000
(3) Na3PO4 + + ++ 1/3 mEq. Na3PO4
V is the burette reading with Ph.th
Na2HPO4
According to Na2HPO4
M.O reading :
HCl Na2HPO4
1/3 mEq. Na3PO4 N × V = 1/2 Wg × 1000
Ew
+
1/2 mEq. Na2HPO4 Wg = 2 × N × V × Ew = ….. g/10mL
1000

V = V { M.O} - V { ph.th}

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An important
summary to identify
the type of mixture

Notes Me.O reading Ph.th reading Phosphate mixture

The two readings are approximately

+ + Na3PO4
similar

No reading for Ph.th + Zero Na2HPO4

There is a reading of both indicators,

++ + (Na3PO4 + Na2HPO4)
but the reading of the Me.O is greater

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Buffer Solutions

Section 5

Buffer solution

Is an aqueous solution of weak acid and its conjugate base or weak

base and its conjugate acid used to resist pH change with added

solute.

A buffer is a pair of weak acid and its salt or weak

base and its salt.

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Importance of buffers

 Buffers are of main importance in regulating the pH of the body

fluids and tissues.

 Many biochemical reactions including those catalyzed by

enzymes require pH control which is provided by buffers.

IMPORTANCE OF PH IN BIOLOGY
 pH affects solubility of many substances.
 pH affects structure and function of most proteins - including
enzymes.
 Many cells and organisms (esp. plants and aquatic animals) can
only survive in a specific pH environment.
 Important point -
pH is dependent upon temperature

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Types of buffers
1. Acidic buffer
Made from a weak acid and its salts

Example:
CH3COOH / CH3COONa
Acetic acid / Acetate

• CH3COOH { weak acid }

• CH3COO-Na { Salt (conjugated base of acetic acid)}

2. Basic buffer
Made from a weak base and its salts

Example:
NH3 / NH4CL
Ammonium hydroxide / Ammonium chloride

• NH3 { weak base }

• NH4Cl
Salt (conjugated acid of ammonium hydroxide)

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EXAMPLES ABOUT BUFFERS

 CH3COOH/ CH3COONa Weak acid/salt buffer

 NH4OH/ NH4Cl Weak base /salt buffer

 H3PO4/NaH2PO4

 NaH2PO4/Na2HPO4 phosphate buffers

 Na2HPO4/Na3PO4

 H2CO3/NaHCO3
carbonate buffers
 NaHCO3/Na2CO3

WAYS TO MEASURE PH
 There are many ways to measure pH such as Indicator dyes and test strips
and pH meter.
 pH meter
 Electrode measures H+ concentration
 Must standardize (calibrate) before using.

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Three practical methods

to prepare a buffer

PREPARATION OF A BUFFER

1- First Method: (Henderson-Hasselbalch equation) Using the buffer pKa, calculate the

amounts (in moles) of acid/salt or base/salt present in the buffer at the desired pH.

2- Second Method: By the Titration, in the presence of one of the two buffer forms with

strong base or acid.

3- The Third Method: Using table

Find a table of the correct amounts of acid/salt or base/salt required for different pH's

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The first method

(Two components)

Molar concentration of acid

Molar concentration of salt

Molar concentration of base

pOH
Molar concentration of salt

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EXAMPLE
PREPARATION OF ACETATE BUFFER

How can you prepare 250 mL of 0.1 M acetate buffer (acetic acid +
sodium acetate), pH 5.2? if you have:
1. Sodium acetate (powder).
2. Acetic acid (1 M).
3. HCl (1 M).
4. NaOH (1 M).

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The steps:
1. Take 2.55 g of sodium acetate and dissolve it in 100 mL water.
2. Add 6.25 mL acetic acid (1 M) and shake well.
3. Add water until 200 mL then measure the pH by pH meter.
4. Adjust the pH of the buffer by adding drops of HCl (1 M) or
NaOH (1 M).
5. Complete with water until 250 ml in a volumetric flask.

The second method

(One component)

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 By the Titration, in the presence of one of the two buffer components with strong
base or acid.

Advantages of this method:

 Easy to understand.
 Useful when only one component of the buffer is available (in this case sodium
acetate)

 In case of sodium acetate present, a strong acid is added (e.g. HCl) until the
required pH is obtained.

CH3COONa+HClCH3COOH+NaCl

So, acetate buffer is formed (CH3COOH/CH3COONa).

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The third method

(Tables)

An example for acetate buffer

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PRACTICAL

39

According to Henderson-Hasselbalch equation,

describe the preparation of phosphate buffer (250
mL, pH=6.9 and 0.3 M), if you have Na2HPO4 and
NaH2PO4 and if you know that pKa = 7.2 and P=
31, Na =23, O=16 and H= 1

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41

21
 Redox reactions
Oxidation & reduction reactions

Sec 6
 Oxidation/Reduction
• A redox reaction is a reaction in which one substance is reduced and
another is oxidized.
• Deals with the movement of ELECTRONS during a chemical
reaction.
• (Oxygen doesn’t have to be present)
 What are oxidation and reduction?
Oxidation and reduction can be used to describe any of the following
processes:

Oxidation Reduction
Addition of oxygen Loss of oxygen
e.g. 2Mg + O2 → 2MgO e.g. 2CuO + C → 2Cu + CO2
Loss of hydrogen Addition of hydrogen
e.g. CH3OH → CH2O + H2 e.g. C2H4 + H2 → C2H6
Loss of electrons Gain of electrons
e.g. Al → Al3+ + 3e- e.g. F2 + 2e- → 2F-
 Electron Transfer Reactions

Oxidation: LOSS of one or more electrons.

Reduction: GAIN of one or more electrons

 Electron Transfer Reactions
• Oxidation & reduction always occur together.
• Electrons travel from what is oxidized towards what is reduced.
• One atom loses e-, the other gains e-
 Redox half equations

• Redox half equations are used to show separately the oxidation and reduction

parts of a redox reaction.

 Half Reaction Method
(Ion/Electron Method)
• Separate equation into two “basic” half reactions

• Balance all atoms except H and O

• Balance oxygen by adding H2O

• Balance hydrogen by adding H1+

• Balance charge by adding electrons to more positive side

• If necessary balance e- by multiplication

• Add together half reactions and simplify

• Check for balance of atoms and charge

Some notes for potassium permanganate
(KMnO4) reactions
• Strong oxidizing agent.
• Non standard material.
(containing impurities of MnO2 – happening auto decomposition when expose
to light or heat).
• Auto indicator.
• Some reactions happen on cold conditions and others on heat.
• Acidic medium is the suitable for the reactions of KMnO4. (H2SO4 dil. Is
used)
• In the beginning of the titration you have to add 2 mL of KMnO4 directly.
 Potassium Permanganate ( KMnO4 )
1. Strong oxidizing agent
• Because electrode potential of redox is +1.55V.

2. Non standard material

• It contains impurities of Mn-oxides.
• After preparation it is getting decomposed by light and
temperature, reacts with water that it was prepared in, then its
concentration will be changed, so it must be kept in brown bottles.
3. Self-indicating reagents
• Because the change of its color is obvious (purple color).
• It is not used as self indicator, but if its concentration decreases to
less than 0.01 N in this case; another external indicator such as
(Diphenylamine (DPA) indicator) will be used with it.

4. Titration without heating such as H2O2, FeSO4 and with heating

such as oxalic acid, oxalate?
• Because heating is related to activation energy and oxalate need
heating to be activated.
5. Its reaction takes place in all medium but the acidic one is used.
In the acidic medium: Manganose (Mn2+) ion will be formed
MnO4- + 5e- Mn2+ + 4H2O

In the neutral medium: it is hard to determine the ending point due to the brown
precipitate from manganese dioxide MnO2.
MnO4- + 3e- MnO2 + 2 H2O

In the Alkaline medium: Green precipitate is formed from manganate MnO42-.

MnO4- + e- MnO42-
6. H2SO4 Sulfuric acid and its peers

• Concentrated H2SO4 is not used because it generates heat that changes

the redox reaction.

• HNO3 can not be used as it is a strong oxidizing agent, so ending point

will be disturbed and the volume of permanganate will be less than the
actual volume.

• HCl can not also be used, it is considered an acid with reducible

properties, so ending point will be disturbed and the volume of
permanganate will be greater than the actual volume.
 Standardization of Potassium permanganate

Oxalic Sodium Oxalate Mohr salt

COONa Ammonium ferrous sulfate
COOH
. 2 H2O (NH4)2Fe(SO4)2·6H2O
COONa
COOH

Oxalate is preferred than oxalic in standardizing permanganate?

The acid contains 2 water molecules, easy to be lost, while oxalate
tolerate heating temperatures up to 100 because it doesn't contain
water crystals.
PRACTICAL

14
1. Standardization of Potassium permanganate KMnO4

Titrant
KMnO4 { N= ???? }

Titrand
10 mL Mohr salt
+
10 mL diluted H2SO4

Colorless Pink
2. Determine number of grams of H2O2 and FeSO4 in 1 L solution.

Titrant Titrations
KMnO4 St. sol.

1 2

Titrand
10 mL H2O2 10 mL FeSO4
+ +
10 mL diluted H2SO4 10 mL diluted H2SO4
Colorless Pink
3. Determine number of grams of oxalic acid in 1 L solution.

Titrant Titration
KMnO4 St. sol.
3

10 mL oxalic acid
Titrand +
10 mL diluted H2SO4,
then heating until the
start of boiling
Colorless Pink
 Titrations
1 2

H2O2 FeSO4
( MnO4- / Mn2+ ) ( H2O2 / O2 ) ( MnO4- / Mn2+ ) ( Fe2+ / Fe3+ )

Reduction - + 8H+ + 5e-

Reduction
( 2) MnO4 - + 8H+ + 5e- Mn2+ + 4H2O ( 1) MnO4 Mn2+ + 4H2O

Oxidant Reduced form Oxidant Reduced form

Oxidation Oxidation
( 5) H2O2
+
O2 + 2H + 2e- ( 5) Fe2+ Fe3+ + e-

Reductant Oxidized form Reductant Oxidized form

MnO4- + 8H+ + 5e- Mn2+ + 4H2O

2 MnO4- + 16H+ + 10e- 2 Mn2+ + 8 H2O
5 Fe2+ 5 Fe3+ + 5e-
5 H2O2 5 O2 + 10 H+ + 10e-
MnO4- + 8H+ + 5 Fe2+ Mn2+ + 4H2O + 5 Fe3+
2MnO4- + 6H+ + 5 H2O2 2Mn2+ + 8H2O + 5 O2
3 Oxalic acid {C2H2O4 }
System
( MnO4- / Mn2+ ) ( C2O42- / CO2 )

Reduction
( 2) MnO4 - + 8H+ + 5e- Mn2+ + 4H2O

Oxidant Reduced form

Oxidation
( 5) C2O4 2- 2CO2 + 2e-

Reductant Oxidized form

2MnO4- + 16H+ + 10e- 2Mn2+ + 8H2O

5 C2O42- 10CO2 + 10e-

2MnO4- + 16H+ + 5C2O42- 2Mn2+ + 8H2O + 10 CO2

 Calculations of Eq.wt
Eq. w of H2O2 = MW = ( 1 X 2) + (16 X 2) = 34 = 17
No. of transferred electrons 2 2

Eq.w of FeSO4 = MW
No. of transferred electrons

= (56 X 1) + (32 X 1) + (16 X 4) = 152 = 152

1 1
Oxalic
acid

KMnO4 oxalic acid

N×V = Wg × 1000
Ew

N×V = Wg × 1000
Ew
Wg = N × V × Ew
1000

then multiply by 100 to calculate the Wg in liter

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Section 7
Redox reactions (continued)

Bichromate, Thiosulfate and

Iodine titrations

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K2Cr2O7 reactions

K2Cr2O7 Potassium bichromate

• Strong oxidizing agent.

• Redox potential +1.33 V

• Standard material.

• Bichromate is less than permanganate as an oxidizing agent because the redox

potential is lower.

• All bicromate titrations are performed in an acidic medium.

• Can not be used as an auto indicator, because the change in color is very slow.

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Bichromate as an oxidant
Cr2O72- + 14 H+ + 6e- Cr3+ + 7H2O

Acidic
medium

The importance of the bichromate interactions

• It is used to adjust sodium thiosulfate solution Na2S2O3 (determine its normal

concentration).
• Used in the titration of ferrous sulfate FeSO4.

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Bichromate titrations
Determination of Determination of normal concentration of
ferrous Na2S2O3 (Indirect titration)

K2Cr2O7 Na2S2O3 (????) N

• 10 mL potassium bichromate
• 10 mL FeSO4 + 10 mL potassium iodide KI
(in excess)
• 10 mL Diluted Sulfuric • 10 mL of diluted sulfuric acid,
Acid titrate until pale yellow
• Add 2 mL of starch and
• Diphenylamine complete the titration from
indicator blue till colorless

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• Why, when adjusting or titrating the thiosulfate

concentration using bichromate, the thiosulfate is not
placed in the conical flask?

• Because thiosulfate dissolves in an acidic medium and the sulfur present

in it is precipitated.

Half ionic equation of thiosulfate

2 S2O32- S4O62- + 2e-

Sodium thiosulfate and

Iodine reactions

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Na2S2O3 Sodium thiosulfate

• Reducing agent.
• Its solution is not stable.
• Easy to decompose in light and oxygen, therefore it is a non-standard
material.

I2 Iodine
• I2 is an oxidizing agent.

• Non-standard material because it is easy to volatilize or sublimate, and

easy to be oxidized in the presence of light, so it is prepared in brown
bottles.

• It is prepared by dissolving it in an excessive amount of potassium iodide

(KI).

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Iod a metry

i
Iod metry Iod o metry

I2 KI
Oxidant Reductant
I 2 + 2 e- 2 I- 2 I- I2 + 2 e-

Titrant
Na2S2O3
i
Iod metry

(0.0211 N)

• 10 mL I2
• Titration with Na2S2O3 till pale yellow then add 3 mL starch till blue
color is appeared
• Then add Na2S2O3 again till colorless

Blue Colorless

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One reaction
System
( S2O32- / S4O62- ) × ( I2 / I - )

I2 + 2 e- 2 I-

2 S2O32- S4O62- + 2e-

I2 + 2 S2O32- 2 I- + S4O62-

Titrant
Na2S2O3
Iod o metry1-1

(0.0211 N)

• 10 mL KMnO4
• 10 mL KI
• 10 mL diluted H2SO4 (5%)
• Titration with Na2S2O3 till pale yellow then add 3 mL starch till blue
color is appeared
• Then Na2S2O3 again till colorless

Blue Colorless

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2 Reactions
First System Second System
( MnO4 / Mn2+ ) × ( I- / I2 )
-
( S2O32- / S4O62- ) × ( I2 / I- )

( × 2) MnO4- + 8 H+ + 5 e- Mn2+ + 4H2O I2 + 2 e- 2 I-

2 S2O32- S4O62- + 2e-

( × 5) 2I- I2 + 2 e-

2 MnO4- + 16 H+ + 10 e- 2 Mn2+ + 8 H2O I2 + 2 S2O32- 2 I- + S4O62-

10 I- 5 I2 + 10e-

2 MnO4- + 16 H+ + 10 I- 2 Mn2+ + 8 H2O + 5 I2

Titrant
Na2S2O3
Iod o metry1-2

(0.0211 N)

• 10 mL K2Cr2O7
• 10 mL KI
• 10 mL diluted H2SO4 (5%)
• Titration with Na2S2O3 till pale yellow then add 3 mL starch till blue
color is appeared
• Then Na2S2O3 again till colorless

Blue Colorless

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2 Reactions
First System Second System
( Cr2O7 2- / Cr3+ ) × ( I- / I2 ) ( S2O32- / S4O62- ) × ( I2 / I- )

Cr2O72- + 14 H+ + 6e- Cr3+ + 7H2O I2 + 2 e- 2 I-

2 S2O32- S4O62- + 2e-

( × 3) 2I- I2 + 2 e-

Cr2O72- + 14 H+ + 6e- Cr3+ + 7H2O I2 + 2 S2O32- 2 I- + S4O62-

6 I- 3 I2 + 6e-

Cr2O72- + 14 H+ + 6 I- Cr3+ + 7H2O + 3 I2

Practical

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1. Determination of Normality and number of grams of Iodine by using

Iodimetry (Direct iodometric titration method ).

2. Determination of Normality and number of grams of Potassium

dichromate by using Iodometry (In-direct iodometric titration method)

3. Determination of Normality and number of grams of Potassium

permanganate by using Iodometry (In-direct iodometric titration method)

Calculations of equivalent weight

Eq.wt = Mwt
Number of transferred electrons

Iodine (I2) = (127 × 2) = 127

2
Potassium dichromate (K2Cr2O7) = ( 39 × 2 ) + ( 52 × 2 ) + ( 16 × 7 ) = 49
6
Potassium permanganate (KMnO4) = ( 39 × 1) + ( 55 × 1 ) + ( 16 × 4 ) = 31.6
5

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Iodine
determinations

No. of grams of Iodine in 1 L

N = Wg
Eq.w X VL

Wg = N× VL× Eq.w = ..….. g/L

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K2Cr2O7
determinations

No. of grams of Potassium bichromate in 1 L

N = Wg
Eq.w X VL

Wg = N× VL× Eq.w = ..….. g/L

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KMnO4
determinations

No. of grams of Potassium permanganate in 1 L

N = Wg
Eq.w X VL

Wg = N× VL× Eq.w = ..….. g/L

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Section 8
Precipitation reactions

Precipitation reactions
They are reactions that depend on precipitation in the assessment of some
substances, whether for the weight of the precipitate (gravimetric
precipitation) or to use it as an indication of the completion of the titration
(volumetric precipitation).

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Usage of precipitation reactions

To determine chloride ion in water sample using

silver nitrate in a neutral medium) (Mohr method).

Silver nitrate AgNO3 is the standard material that is used

in precipitation titrations

Why acidic or basic media are not used in silver nitrate

reactions?
In Alkaline medium:
Because silver nitrate reacts with the alkaline medium, then sodium chloride,
then the indicator, and thus a greater quantity is consumed than the actual
equivalent amount of chlorine ions:
AgNO3 + NaOH AgOH
In Acidic medium:
Silver nitrate reacts with potassium chromate (K2CrO4) (the indicator) and
forms chromic acid, so there will be no indicator that is responsible for
determining the reaction ending point.

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Practical

Determine number of grams of chloride ion in the bottle you have.

Titrant
AgNO3
( N = 0.0722 N )

Titrand
10 mL NaCl
+
1 mL potassium chromate
(K2CrO4)

Yellow Buff precipitate

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Reaction
(Silver nitrate in neutral medium )

AgNO3 + NaCl AgCl + NaNO3

White precipitate

The extra one drop from AgNO3 will react with K2CrO4

AgNO3 + K2CrO4 Ag2CrO4

Buff precipitate

Calculations

milli Eq. AgNO3 = milli Eq. Cl-

N × V = Wg × 1000
Eq.w

18