Chem 1221 Module 6 PDF

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CHE 1221
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REF SEA-BSCHE-CHE526-2020
MODULE 6: VOLUMETRIC METHODS OF ANALYSIS:UNIT 1: ACIDIMETRY AND

ALKALIMETRY
UNIT 1: INTRODUCTION: TITRATION CONCEPTS
QUANTITATIVE ANALYSIS
DIVISIONS OF ANALYTICAL CHEMISTRY:
a. Qualitative Analysis - nature of the constituents of a given material

– identification of constituents present in a sample
b. Quantitative Analysis - proportion in which these constituents are present
-measures the mass of a substance chemically related to the

analyte
DIVISIONS OF QUANTITATIVE ANALYSIS:

1. Volumetric Analysis - measures the volume of a standard reacting reagent with
the desired constituent in a definite chemical reaction
- commonly known as “TITRATION”
2. Gravimetric Analysis - based entirely upon weight, the original substance

is
weighed and from it the constituent to be determined is isolated as an element or as
a compound of definite composition

3. Colorimetric Method - the substance to be determined is converted to
some compound which imparts to its solution a distinct color, the intensity of which
varies in proportion to the amount of a compound in a solution
4. Other physicochemical Methods - quantities of constituents from

measurements of such properties as the turbidity of suspensions of semi colloidal
precipitate
5. Gas Volumetric Methods - determination of a mixture of gases
VOLUMETRIC ANALYSIS
Divisions:
1. Neutralization methods – acidimetry (acid determination) and alkalimetry (alkali

determination)
2. Oxidation and Reduction – “redox” – oxidimetry and reductimetry
3. Precipitation methods – precipitimetry
4. Complex formation methods - compleximetry
Definition of terms:
Titration – determination of the concentration (unknown) of a solution by the

gradual
addition of a standard (known) solution
titrant – solution of known concentration (reagent solution)
analyte – substance under study (substance being titrated)
Standard solution – solution whose concentration is accurately known

a. standard acid solutions:
HCl, HNO3, H2SO4, H2C2O4
b. standard alkali solutions:

NaOH, KOH, Ba(OH)2
Standardization – process of determining the exact concentration of a titrant
Primary standard – a substance of highest purity used for standardization
characteristics: highest purity, soluble in water, stable towards air, high temp
and humidity
example: potassium hydrogen phthalate (KHP) or KHC8H4O4 ; sodium

carbonate, sulfuric acid
Indicator – a substance (colored dye) that is sensitive hydrogen ion concentration,

changes in color once the end point is reached (from acidity to alkalinity and vice
versa)
example: phenolphthalein, methyl orange, congo red, bromocresol

green, litmus paper
• Endpoint – point in titration where the color of the indicator changes which
coincides with the EQUIVALENCE POINT
• Equivalence point – the point in titration in which the chemical reaction is

completed or
the point of complete neutralization
- point where the acid and the base added in amounts are
equivalent to
each other

• Normality = equivalents of solute / liter of solution
• equivalents, E = weight of solute .
equivalent weight of solute
also: equivalents,E = N X V in liters
Note: N = eq/ L = meq/mL
NEUTRALIZATION - a reaction between a base and an acid to form salt and water.
base + acid → salt + water
ex. NaOH + HCl → NaCl + water
Equivalent weights in Neutralization Methods
fundamental reaction of acidimetry and alkalimetry is:
H+ + OH- H2O
- the neutralization of an acid by a base or the neutralization of a base by an acid
• equivalent weight of a substance acting as an acid is that weight of it which is

equivalent in total neutralizing power to one mole of Hydrogen as H +
• Equivalent weight of a substance acting as a base is that weight of it which will

neutralize one mole of hydrogen ions (or equivalent in total neutralizing power to
one mole of hydroxyl ions, OH-)
equivalent weight of solute = molecular weight
factor
Recall: factor determination:
acid – the number of H+ replaceable
HCl f=1 H2SO4 f=2
HC2H3O2 f=1 H3PO4 f=3
base – the number of OH- replaceable
NaOH f=1 Al(OH)3 f=3
Ca(OH)2 f=2
Others: needed in precipitimetry, redox, compleximetry
salt – the total positive charge

NaCl f=1 Na3PO4 f=3
Na2SO4 f=2
redox – change in oxidation state
Mn+2 Mn+7 f=5

S+6 S-2 f=8
DETERMINATION OF NORMALITY OF SOLUTION
g solute
N = eq. wt solute
liter solution
eq. wt = MW solute / f
or N = W (g) solute x f solute

MW solute x L solution
WORKING FORMULA:
equivalents of acid = equivalents of base
or milliequivalents of acid = milliequivalents of base
meq a = meq b
me liquid = V mL x N , meq/mL
me solid = w (g) solid

MW
f(1000)
equivalents = N in eq/L X V in L
3 CONDITIONS IN TITRATION:
(1) 1 LIQUID / 1 LIQUID

meq a = meq b
V a x Na = Vb x Nb
(2) 1 LIQUID / 1 SOLID

meq a = meq b
V a x Na = w(g) solid
MW
f(1000)

3. 1 SOLID / 1 SOLID
meq a = meq b
w(g) a = w(g) b
MW a MW b
fa(1000) fb(1000)
Ex. How many grams of each of the following solutions constitute the g-equiv wt as
an acid assuming complete neutralization unless otherwise stated
a. HNO3
b. KHSO4
c. H2SO3
d. H2C2O4.2H2O
e. CH3COOH
f. P2O5 – forming H2PO4-1
g. SO3 (acid fr H2SO4)
Soln:
Equivalents = g - equivalents
g-equiv wt = equiv wt
Whatever will be the equiv –wt will be the gram ( stated fr the problem)
Basis: a g-equiv wt of a subst acting as an acid is that number of g of the subst which in
neutralization process furnishes one g-atom(1.0089) of replaceable hydrogen:
𝑀𝑊𝑎𝑐𝑖𝑑
𝑔 − 𝑒𝑞𝑢𝑖𝑣 𝑤𝑡 =
𝑓𝑎𝑐𝑖𝑑
𝑔
63.02𝑚𝑜𝑙 𝑔
a. 𝐻𝑁𝑂3 = 𝑒𝑞 = 63.02 = 63.02 𝑔
1𝑚𝑜𝑙 𝑒𝑞
𝑔
136.17 𝑔
𝑚𝑜𝑙
b. 𝐾𝑆𝐻𝑂4 = 𝑒𝑞 = 136.17 = 136.17 𝑔
𝑔
82.08𝑚𝑜𝑙 𝑔
c. 𝐻2 𝑆𝑂4 = 𝑒𝑞 = 41.04 = 41.04 𝑔
ASSIGNMENT: 1. d,e,f,g
Ex.2 What is the millieqquivalent wt of each of the ff subst acting as bases with complete
neutralization in each case
a. 𝐶𝑎 (𝑂𝐻)2 f. 𝑍𝑛𝑂
b. 𝐵𝑎𝑂 g. 𝐶𝑎𝐶𝑂3
c. 𝐾𝐻𝐶𝑂3 h. 𝐹𝑒2 𝑂3

d. 𝑁𝑎2 𝑂
e. 𝑁𝑎2 𝑂2
𝑀𝑊 𝑔 − 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑤𝑡 𝑜𝑓 𝑏𝑎𝑠𝑒
𝑚𝑖𝑙𝑙𝑖𝑒𝑞𝑢𝑖𝑣 𝑤𝑡(𝑚𝑒 𝑤𝑡) = =
𝑓(1000) 1000 𝑚𝐿
𝑔
74.1𝑚𝑜𝑙
a. 𝐶𝑎 (𝑂𝐻)2 = 𝑒𝑞 𝑚𝑒𝑞 = 0.03705
2𝑚𝑜𝑙(1000 )
𝑒𝑞
𝑔
153.34𝑚𝑜𝑙
b. 𝐵𝑎𝑂 = 𝑒𝑞 𝑚𝑒𝑞 = 0.07667
2𝑚𝑜𝑙(1000 )
𝑒𝑞
𝑔
100.12𝑚𝑜𝑙
c. 𝐾𝐻𝐶𝑂3 = 𝑒𝑞 𝑚𝑒𝑞 = 0.1002
1𝑚𝑜𝑙(1000 )
𝑒𝑞
ASSIGNMENT 2: d,e,f,g,h
MIXING PROCESSES:
CASE I: solution B (acid)
Solution A (acid) Resulting solution (R.S )
(acid)
Solution C (acid)
meq A (acid) + meq B (acid) + meq C (acid) = meq R.S. (acid)
A, B, C & R.S. could be bases too..
Note: meq pure water = 0
CASE II:
- Solutions mixed are different (1.e. acids and bases)

Solution B (base)
Solution A (acid) Resulting solution

(either acidic or basic depending on
total meq acid & total meq base)
Solution C (base)
R.S is acidic if total meq acid > total meq base

R.S is basic if total meq acid < total meq base
Example: If 3.00 g of solid KOH and 5.00 g of solid NaOH are mixed, dissolved in water, and
the solution made up to 1500 mL, what is the normality of the solution as a base?
Given: W KOH = 3.00 g V soln = 1500 mL

W NaOH = 5.00 g
Reqd: N
Soln:
Tot eq of base = eq KOH + eq NaOH

N = eq/L
eq of KOH = 3.00 g KOH = 0.0535 eq

(56.1 g/mol)/1(eq/mol)
eq of NaOH = 5.00 g NaOH = 0.125 eq

(40.0 g/mol)/ 1(eq/mol)
N= (0.0535 + 0.125) = 0.1189 eq/L

1500 mL (1L/1000mL)
Adjusting a Solution to a desired Normality

- dilution concept
Example: To what volume must 750 mL of 2.400 N solution be diluted in order to make it
1.760 N?
Given:
V1 = 750 mL
C1 = 2.400 N C2 = 1.760 N
Reqd: V2
Soln:
V 1 C1 = V2 C2
(750 mL)(2.400 meq/mL) = V2 (1.760 meq/mL)
V2 = 1023 mL

*add 273 mL of water to make 1023 mL of a 1.76N
Soln
Example: How much 0.600 N base must be added to 750 mL of a 0.200 N base in order for
the solution to be 0.300N?
Given:
Solution A(base) Resulting solution

0.600 N (ei 0.300N
Solution B (base)
750 mL ,0.200 N
V1C1 + V2C2 = VmCm

V1(0.6meq/mL) + (750ml x 0.2meq/mL) = (750 + V1)(0.3meq/mL)
V1 = 250 mL
Example: A solution containing 25.3 mL of 0.1065 N HCl is added to one containing 92.2
mL of 0.2715 M H2SO4 and 50.0 mL of 1.00 N KOH are added. Is the solution acid or alkaline?
What volume of 0.100N acid or alkali must be added to neutralize the soln?
50mL KOH
1N
25.3 mL
0.1065 N HCl
Resulting solution , RS
92.2 mL
0.2715 M H2SO4
Soln:
a. if the total me acid> tot me base ; the RS is acid
b. . if the total me acid< tot me base ; the RS is base
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒𝑞 𝑎𝑐𝑖𝑑𝑠 = 𝑚𝑒𝑞 𝐻𝐶𝑙 + 𝑚𝑒𝑞 𝐻2𝑆𝑂4
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒𝑞 𝑎𝑐𝑖𝑑𝑠 = 𝑉𝐻𝐶𝑙 𝑁𝐻𝐶𝑙 + 𝑉𝐻2 𝑆𝑂4 𝑁𝐻2 𝑆𝑂4

For the unit of Normality, N it can be eq/L or me/mL
Since we are given the concentration of H2SO4 in M , convert it to N by using the

formula : N = M x f
N = 0.2715 mol/L X 2 eq/mol = 0.543 eq/L or meq/mL
𝑚𝑒𝑞 𝑚𝑒𝑞
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒 𝑎𝑐𝑖𝑑𝑠 = (25.3 𝑚𝐿) (0.1065 ) + (92.2 𝑚𝐿) (0.543 ) = 52.76 𝑚𝑒
𝑚𝐿 𝑚𝐿
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒 𝑏𝑎𝑠𝑒 = 𝑚𝑒 𝐾𝑂𝐻

𝑚𝑒𝑞
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒 𝑏𝑎𝑠𝑒 = (50 𝑚𝐿) (1 ) = 50 𝑚𝑒
𝑚𝐿
52.76 𝑚𝑒𝑞 > 50𝑚𝑒𝑞 ∴ 𝑅𝑆 𝑖𝑠 𝑎𝑐𝑖𝑑𝑖𝑐
b. for neutralizing the RS

𝑛𝑒𝑡 𝑚𝑒𝑞 𝑅𝑆 𝑎𝑠 𝑎𝑐𝑖𝑑 = 𝑚𝑒𝑞 𝑏𝑎𝑠𝑒
OR:
𝑡𝑜𝑡 𝑚𝑒𝑞 𝑎𝑐𝑖𝑑 = 𝑚𝑒𝑞 𝑏𝑎𝑠𝑒

Na Va = Nb Vb
(25.3 mL)(0.1065 N) + (92.2mL)(0.543N) = (V)(0.1N) + (50mL)(1N)
V= 27.60 mL
Neutralization – the reaction between an acid and a base to form water and salt
Ex. NaOH + HCl ⟶ HOH + NaCl
Example: Given the ff data: 1.00 mL of NaOH ≎ 1.117 mL HCl, the HCl is 0.4876 N. How
much water should be added to 100 mL of the alkali to make it 0.500 N
Given: V NaOH = 1.00mL V HCl = 1.117 mL

N HCl = 0.4876 N
Reqd; V H2O
Soln:
me NaOH = me HCl
(𝑁𝑁𝑎𝑂𝐻 )(𝑉𝑁𝑎𝑂𝐻 ) = (𝑁𝐻𝐶𝑙 )(𝑉𝐻𝐶𝑙 )

(𝑁𝑁𝑎𝑂𝐻 )(1.00𝑚𝐿) = (0.4876 𝑁)(1.117𝑚𝐿)
𝑁𝑁𝑎𝑂𝐻 = 0.5446 𝑁

(𝑉1 )(𝐶1 ) = (𝑉2 )(𝐶2 )
(100𝑚𝐿)(0.5446𝑁) = (𝑉2 )(0.5𝑁)

𝑉2 = 108.92 𝑚𝐿
𝑉𝐻2 𝑂 = 𝑉2 − 𝑉1 = 108.92 − 100 = 8.92 𝑚𝐿
Example: If 30.00 g KHC2O4. H2C2O4 ( potassium tetroxalate, Ktet) are dissolved ,diluted to
1000 mL, and it is found that 40.00 mL are neutralized by 20.0 mL of a solution of KOH, what
is the normality of the alkali solution?
Given: W Ktet = 30.00 g V Ktet = 40 mL

V soln = 1000 mL, V KOH = 20.00 mL
Reqd: N KOH
Soln:
We are given the wt and volume of potassium tetroxalate solution, so we can solve for the
concentration in N by using the formula:
𝑊 ×𝑓
𝑁 = 𝑀𝑊 × 𝑉
𝑒𝑞
30.0 𝑔 ×3 𝑚𝑜𝑙
𝑁 𝐾𝑡𝑒𝑡 = 𝑔 = 0.354 𝑁
242.2𝑚𝑜𝑙 × 1𝐿
In neutralization process , we are given the volume of Ktet to neutralize KOH
meq acid = meq base

𝑚𝑒𝑞 KHC2O4.H2C2O4 = 𝑚𝑒𝑞 𝐾𝑂𝐻
(𝑁 × 𝑉 )𝐾𝑡𝑒𝑡 = (𝑁 × 𝑉 )𝐾𝑂𝐻
(0.354 𝑁)(40𝑚𝐿) = (𝑁)(20𝑚𝐿)
𝑁𝐾𝑂𝐻 = 0.708 𝑁
Example: a sample of pure oxalic acid, H2C2O4.2H2O weighs 0.2000 g and requires 30.12 mL
of KOH solution for complete neutralization. What is the N of the KOH solution?
Given:
W H2C2O4.2H2O = 0.2000 g V KOH = 30.12 mL
Reqd: N KOH
Soln:
Eq acid = eq base
Eq H2C2O4.2H2O = eq KOH
weight oxalic x factoroxalic = NKOH VKOH

MWoxalic acid

0.2000 g x 2 eq/mol = 30.12 mL X NKOH
126.07 g/mol 1000 mL/L
NKOH = 0.1053 eq/L
Example: What is the normality of a solution of HCl if 20.00 mL is required to neutralize the
NH3 that can be liberated from 4.00 millimoles of (NH4)2SO4?
Given:
V HCl = 20.00 mL
(NH4)2SO4 = 4.00 millimoles
Reqd: N HCl
Soln:
Eq Base = Eq acid
Eq NH3 = Eq HCl
weightb x factorb = NHCl VHCl

MWb
molb x factorb = NHCl VHCl
4.00 mmol (NH4)2SO4 x 2mmol NH3 = 8 mmols NH3

1mmol (NH4)2SO4
8 mmols NH3 x 1 meq = 20.00 mL (NHCl)

mmol
NHCl = 0.400 meq/mL
STANDARDIZATION OF ACID AND BASE
Standard acid solutions

- Prepared from HCl, HNO3 , H2SO4 , oxalic acid
Standard alkali solutions
- NaOH, KOH, Ba(OH)2
the standardization of a solution of an acid

- determine the volume of an acid which is equivalent to a known weight of a
pure basic substance
the standardization of a solution of a base
- determine experimentally the volume of a base which is equivalent to a known
weight of a pure acid

ex. In standardizing solution of HCl it is found that 47.26 mL of the acid are
equivalent to 1.216 g of pure Na2CO3( methyl orange indicator).What is the
Normality of the acid?
Given:
V HCl = 47.26 mL
W Na2CO3 = 1.216 g
Reqd: N HCl
Soln;
meq acid = meq base

𝑚𝑒𝑞 HCl = 𝑚𝑒𝑞 𝑁𝑎2 𝐶𝑂3
(𝑊𝑁𝑎2 𝐶𝑂3 )
(𝑁 × 𝑉 )𝐻𝐶𝑙 = 𝑀𝑊
𝑓 ×1000
(1.216 𝑔)
( 𝑁)(47.26𝑚𝐿) =
105.99 𝑔/𝑚𝑜𝑙
2 𝑒𝑞/𝑚𝑜𝑙 × 1000
𝑁𝑁𝑎2 𝐶𝑂3 = 0.4856 𝑁
BACKTITRATION
– when there is over addition of a titrant at the endpoint, a standard solution

(backtitrant) is added to neutralize the over added titrant until a color change is
indicated
Example:
A solution of sulphuric acid is standardized against a sample which has been previously
found to contain 92.44% CaCO3 and no other basic material. The sample weighing
0.7423g is treated with 42.42mL of the acid then required 11.22 mL of NaOH solution.
If 1.00 mL of the acid is equivalent to 0.9976 mL of the NaOH, what is the normality of
each?
Standardization of acid: 1mL base ≎ X ml base

1mL H2SO4 ≎ 0.9976 mL NaOH
1 𝑚𝐿 𝐻2 𝑆𝑂4 0.9976 𝑚𝐿 𝑁𝑎𝑂𝐻
=
𝑥 𝑚𝐿 𝐻2 𝑆𝑂4 11.22 𝑚𝐿 𝑁𝑎𝑂𝐻
mL 𝐻2 𝑆𝑂4 = 11.2469
net Volume H2SO4 = 42.42 - 11.2469 = 31.17301 mL
𝑚𝑒 𝐶𝑎𝐶𝑂3 = 𝑚𝑒 𝐻2 𝑆𝑂4

(𝑊𝐶𝑎𝐶𝑂3 )
𝑀𝑊 = 𝑁 𝐻2 𝑆𝑂4 × 𝑉𝐻2 𝑆𝑂4
𝑓 ×1000
𝑤𝑡 𝑠𝑢𝑏𝑠𝑡
To calculate for the wt of CaCO3: % 𝑤𝑡 = × 100
𝑤𝑡 𝑠𝑎𝑚𝑝𝑙𝑒
92.44%
(0.7423 𝑔)( )
100
100.08 𝑔/𝑚𝑜𝑙 = 𝑁 𝐻2 𝑆𝑂4 × 31.17 𝑚𝐿
2 𝑒𝑞/𝑚𝑜𝑙 ×1000
𝑁 𝐻2 𝑆𝑂4 = 0.4399𝑁
𝑚𝑒 𝑁𝑎𝑂𝐻 = 𝑚𝑒 𝐻2 𝑆𝑂4
1mL H2SO4 ≎ 0.9976 mL NaOH

Therefore in 1 mL NaOH ≎ 𝑥 𝑚𝐿 𝐻2 𝑆𝑂4
1𝑚𝐿
𝑚𝐿 𝐻2 𝑆𝑂4 = = 1.0024 𝑚𝐿
0.9976
(1𝑚𝐿 )(𝑁𝑁𝑎𝑂𝐻 ) = (1.0024 𝑚𝑙)(0.4399𝑁)
𝑁𝑁𝑎𝑂𝐻 = 0.4409 𝑁
Example: When CaCO3 is used as a standard for a strong acid, it is necessary to dissolve it
in an excess of the acid and back titrate with NaOH solution. In such a standardization, a
water suspension of 1.000 g of CaCO3 was used. A volume of 49.85 mL of HCl was added
from a buret, and warming the solution to remove any
dissolved CO2, the solution required 6.32 mL NaOH to reach an endpoint. If a separate 50.0
mL pipetful of the HCl required 48.95 mL of the NaOH for neutralization, what is the N of the
HCl and of the NaOH?
eq CaCO3 = eq HCL – eq NaOH

wt CaCO3 x factor CaCO3 = NHCl VHCl – NNaOH VNaOH
MW CaCO3
1.000g x 2 eq/mol = 49.85mL NHCl – 6.32mL NNaOH
100.08 g/mol
equation 1
But me HCl = me NaOH
50.0ml NHCl = 48.95mL NNaOH equation 2
NHCl = 48.95mL NNaOH
50.0 mL
NHCl = 0.4605 N NNaOH = 0.4704 N
Assignment:
3. How many mL of 0.1421N KOH are required to neutralize 13.72 mL of 0.06850 M
H2SO4?

4. Given the ff data: 1.00 mL≎ 1.117 mL HCl, the HCl is 0.4876 N. How much water
should be added to 100 mL of the alkali to make it 0.500 N?
5. A solution of H2SO4 is found to be 0.5172 N and 39.65 mL of it are equivalent to 21.74
mL of standard alkali solution. What is the N of the alkali and how many grams of
sulfamic acid (HSO3.NH2) will 1.oo mL of it neutralize?
6. In standardizing a solution of NaOH against 1.431g of KHC 8H4O4, the analyst uses
35.50 mL of the alkali and has to run back with 5.12 mL of acid ( 1mL ≎0.0031g Na2O)
What is the normality of NaOH?
7. A solution of H2SO4 is standardized against a sample of which has been previously
found to contain 92.44% CaCO3 and no other basic material. The sample weighing
0.7423 g is treated with 42.42 mL of the acid and the excess acid then requires 11.22
mL of NaOH solution. If 1.00 mL of the acid is equivalent to 0.9976 mL of the NaOH,
what is the N of each solution?
8. - If 44.97 mL of a solution of HCl are equivalent to 43.76 mL of a solution of NaOH,
and if 49.14 mL of the latter will neutralize 0.2162 g of KHC2O4.H2C2O4.2H2O, what
volume of water should be added to 100 mL of the HCl in order to prepare a mixture
which is 0.0500 N as an acid?
9. What is the equivalent weight of an organic acid if 44.00 mL NaOH solution (1.000
mL ≎ 1.100 mL HCl ≎ 0.01001 g CaCO3) are required to neutralize 0.5192 g of the
organic acid?
DETERMINATION OF TOTAL ACIDITY AND ALKALINE STRENGTH
Calculation of Percent Purity from Titration Values
Na V a = Nb V b
weight a x factora = Nb Vb 1
MWa
weight a = Nb Vb x MWa
factora
% component (a) = weighta x 100 2
weight of sample
% component (a) = Nb Vb x MWa x 1 x100
factora wt sample

Example: A sample of pearl ash (technical grade of K2CO3) weighing 2.000 g is titrated with
HCl and requires 25.00 mL. What is the alkaline strength of the ash in terms of percent K 2O if
20.00 mL of the HCl will just neutralize the NH3 that can be liberated from 4.000 mmols of
(NH4)2HPO4?
Given:
Wt sample = 2.000 g V HCl = 20.0 mL
V HCl = 25.0 mL (NH4)2HPO4= 4.000 mmols
Reqd: % K2O
Soln:
me K2O = me HCl
meq HCl = me (NH4)2HPO4
20.00 mL (NHCl) = 4 mmols x 2 meq/mmol
NHCl = 0.400 me/mL
weight K2O x 2 me/mmol = 25.00 mL(0.40 me/mL)

94.20 mg/mmol
Weight K2O = 471 mg or 0.471 g

% K2O = 0.471 g x 100 = 23.55%
2.00 g
Example: On ignition, rochelle salt, KNaC4H4O6.4H2O, is converted to KNaCO3. A sample of

the original salt weighs 0.9546 g, and the ignition product is titrated with H 2SO4. From the ff
data find the % purity of the sample: H2SO4 used = 41.72 mL; 10.27 mL H2SO4 ≈ 10.35 mL
NaOH; the NaOH is 0.1297N; NaOH used for back titration = 1.91 mL
me KNaC4H4O6.4H2O = me H2SO4 – me NaOH(back titration)

me H2SO4 = me NaOH
10.27mL (NH2SO4) = 10.35 mL (0.1297 N)
NH2SO4 = 0.1307 N
wt KNaC4H4O6.4H2O x 2 me/mmol
282.19 mg/mmol
= 0.1307N(41.72 mL) – 0.1297N(1.91 mL)
wt KNaC4H4O6.4H2O = 734.41 mg = 0.73441 g
% purity = (0.73441/ 0.9546) = 76.93%

Example: What weight of soda ash should be taken for analysis such that the percentage
of Na2O present can be found by multiplying by 2 the number of milliliters of 0.200 N acid
solution used in titration?
factora
% component (a) = weighta x 100
weight of sample
factora wt sample
% Na2O = 2 x (Vacid)
2 x (Vacid) = 62 mg/mmol x (0.200 me/ml)(Va) x 1 .
2 me/mmol wt sample
weight sample = 0.3100 g
Example: A sample of pearl ash (technical grade of K2CO3) weighing 2.000 g is titrated with
HCl and requires 25.00 mL. What is the alkaline strength of the ash in terms of percent K 2O if
20.00 mL of the HCl will just neutralize the NH3 that can be liberated from 4.000 mmols of
(NH4)2HPO4?
me K2O = me HCl
meq HCl = me (NH4)2HPO4
20.00 mL (NHCl) = 4 mmols x 2 meq/mmol
NHCl = 0.400 me/mL
weight K2O x 2 me/mmol = 25.00 mL(0.40 me/mL)
94.20 mg/mmol
Weight K2O = 471 mg or 0.471 g
% K2O = 0.471 g x 100 = 23.55%
2.00 g
Example: On ignition, rochelle salt, KNaC4H4O6.4H2O, is converted to KNaCO3. A sample of

the original salt weighs 0.9546 g, and the ignition product is titrated with H2SO4. From the ff
data find the % purity of the sample: H2SO4 used = 41.72 mL; 10.27 mL H2SO4 ≈ 10.35 mL
NaOH; the NaOH is 0.1297N; NaOH used for back titration = 1.91 mL
me KNaC4H4O6.4H2O = me H2SO4 – me NaOH(back titration)

me H2SO4 = me NaOH
10.27mL (NH2SO4) = 10.35 mL (0.1297 N)
NH2SO4 = 0.1307 N
wt KNaC4H4O6.4H2O x 2 me/mmol
282.19 mg/mmol
= 0.1307N(41.72 mL) – 0.1297N(1.91 mL)
wt KNaC4H4O6.4H2O = 734.41 mg = 0.73441 g
% purity = (0.73441/ 0.9546) = 76.93%

Example: What weight of soda ash should be taken for analysis such that the percentage
of Na2O present can be found by multiplying by 2 the number of milliliters of 0.200 N acid
solution used in titration?
factora
% component (a) = weighta x 100
weight of sample
factora wt sample
% Na2O = 2 x (Vacid)
2 x (Vacid) = 62 mg/mmol x (0.200 me/ml)(Va) x 1 .
2 me/mmol wt sample
weight sample = 0.3100 g
INDIRECT VOLUMETRIC METHOD

- calculation is made by determining the total number of milliequivalents of reagent
added and subtracting the number of milliequivalents used in titration – the difference in
the number is the number of milliequivalents of desired substance
substance reagent
determined added
+ products
A A
B
Titrated
amount
Example: A sample of meat scrap weighing 2.000 g is digested with concentrated H 2SO4
and a catalyst. The resulting solution is made alkaline with NaOH and the liberated
ammonia distilled into a 50.0 mL of 0.6700 N H 2SO4. The excess then requires 30.10 mL of
0.6520 N NaOH for neutralization. What is the percentage of nitrogen in the meat?
Example: A sample of meat scrap weighing 2.000 g is digested with concentrated H 2SO4
and a catalyst. The resulting solution is made alkaline with NaOH and the liberated
ammonia distilled into a 50.0 mL of 0.6700 N H 2SO4. The excess then requires 30.10 mL of
0.6520 N NaOH for neutralization. What is the percentage of nitrogen in the meat?
Given:
Wt sample = 2.000 g V NaOH = 30.10 mL
V H2SO4 = 50.0 mL N NaOH = 0.6520 N
N H2SO4= 0.6700 N
Reqd: %N

Soln:
Kjeldahl method – determination of N in organic matl
meq H2SO4 = 50.0 mL x 0.6700 meq/mL = 33.50 me

meq NaOH = 30.10 mL x 0.6520 meq/mL = 19.62 me
Difference in meq = 13.88 me

- this is the meq of H2SO4 that reacted with NH3 in the meat
weight a x factora = Nb V b
MWa
meq NH3 = meq H2SO4

weightNH3 x 1 me/mmol = 13.88 me
17 mg/mmol MW of NH3
At wt N
weight NH3 = 235.96 mg/1000mg/g = 0.23596 g
weight N = 0.23596 g NH3 x 1mol NH3 x 1mol N x 14gN = 0.19432 g
14g NH3 1mol NH3 1mol N
Or meq N = meq NH3 = meq H2SO4

weight N x 1 me/mmol = 13.88 me
14 me/mmol
wt N = 0.19432 g
%N = 0.19432 g x 100 = 9.716%

2.000 g
Example: When a direct current is passed through a solution of NaCl, using metallic Hg as a
cathode, a compound having the formula NaHg2 is formed as an amalgam in the Hg. It is
used as a powerful reducing agent. A sample of the material weighing 5.00 g is added to
water and after the evolution of H2 ceases, the resulting solution requires 40.75 mL of 0.1067
N HCl for titration. a) Write an equation for the action of the amalgam and b) calculate
the percentage of Na in the sample.
a) 2NaHg2 + 2H2O 2NaOH + 4Hg + H2
b) me Na = me NaHg2 = me HCl
weight Na x 2 me/mmol = 40.75 mL (0.1067 N)
2(23) mg/mmol
weight Na = 100 mg = 0.0100 g
% Na = (0.010 g /5.00 g) x 100 = 2.00%

Assignment:
16- If all the N in 10.0 mmols urea, CO(NH2)2, is converted to NH4HSO4, and if with excess
NaOH the NH3 is evolved and caught in 50.0 mL of HCl (1.00 mL ≈ 0.03000 g CaCO 3), what
volume of NaOH (1.00 mL ≈ 0.3465 g H2C2O4.2H2O) would be required for complete
titration?
17- The percentage of protein in meat products is determined by multiplying the %N as
determined by the kjeldahl method by the arbitrary factor 6.25. A sample of processed
meat scrap weighing 2.000 g is digested with concd H 2SO4 and Hg (catalyst) until the N
present has been converted to NH4HSO4. This is treated with excess NaOH, and the
liberated NH3 is caught in 50.0 mL pipetful H2SO4 (1.000 mL ≈ 0.01860 g Na2O). The excess
acid requires 28.80 mL NaOH (1.000 mL ≈ 0.1266 g KHP). Calculate % protein in the meat
scrap.
18- A 2.00 g sample of steel is burned in O2, and the evolved CO2 after passing through
appropriate purifying trains is caught in 100 mL Ba(OH)2 solution. The supernatant liquid
requires 75.0 mL HCl (1.00 mL ≈ 0.00626 g Na 2CO3 , 1.00 mL ≈ 1.12 ml Ba(OH)2 ). What is the
% Carbon in the steel?
Assignment:
19- A sample of limestone is titrated for its value as a neutralizing agent. A sample weighing
1.000 g is taken. What must be the normality of the titrating acid so that every 10 ml will
represent 4 ½ % of the neutralizing value expressed in terms of percentage of CaO.
20- What weight of soda ash must be taken for analysis so that by using 0.5000N HCl for
titrating, (a) buret reading will equal the percentage of Na 2O, (b) three times the buret
reading will equal the percentage of Na 2O, (c) every 3 mL will represent 1% Na2O (d) each
mL will represent 3% Na2O (e) the buret reading and the percentage of Na2O will be in the
respective ratio 2:3?
Example: When a direct current is passed through a solution of NaCl, using metallic Hg as a
cathode, a compound having the formula NaHg2 is formed as an amalgam in the Hg. It is
used as a powerful reducing agent. A sample of the material weighing 5.00 g is added to
water and after the evolution of H2 ceases, the resulting solution requires 40.75 mL of 0.1067
N HCl for titration. a) Write an equation for the action of the amalgam and b) calculate
the percentage of Na in the sample.
c) 2NaHg2 + 2H2O 2NaOH + 4Hg + H2
d) me Na = me NaHg2 = me HCl
weight Na x 2 me/mmol = 40.75 mL (0.1067 N)
2(23) mg/mmol
weight Na = 100 mg = 0.0100 g
% Na = (0.010 g /5.00 g) x 100 = 2.00%
Assignment:
16- If all the N in 10.0 mmols urea, CO(NH2)2, is converted to NH4HSO4, and if with excess
NaOH the NH3 is evolved and caught in 50.0 mL of HCl (1.00 mL ≈ 0.03000 g CaCO 3), what
volume of NaOH (1.00 mL ≈ 0.3465 g H2C2O4.2H2O) would be required for complete
titration?

17- The percentage of protein in meat products is determined by multiplying the %N as
determined by the kjeldahl method by the arbitrary factor 6.25. A sample of processed
meat scrap weighing 2.000 g is digested with concd H 2SO4 and Hg (catalyst) until the N
present has been converted to NH4HSO4. This is treated with excess NaOH, and the
liberated NH3 is caught in 50.0 mL pipetful H2SO4 (1.000 mL ≈ 0.01860 g Na2O). The excess
acid requires 28.80 mL NaOH (1.000 mL ≈ 0.1266 g KHP). Calculate % protein in the meat
scrap.
18- A 2.00 g sample of steel is burned in O2, and the evolved CO2 after passing through
appropriate purifying trains is caught in 100 mL Ba(OH)2 solution. The supernatant liquid
requires 75.0 mL HCl (1.00 mL ≈ 0.00626 g Na 2CO3 , 1.00 mL ≈ 1.12 ml Ba(OH)2 ). What is the
% Carbon in the steel?
Assignment:
19- A sample of limestone is titrated for its value as a neutralizing agent. A sample weighing
1.000 g is taken. What must be the normality of the titrating acid so that every 10 ml will
represent 4 ½ % of the neutralizing value expressed in terms of percentage of CaO.
20- What weight of soda ash must be taken for analysis so that by using 0.5000N HCl for
titrating, (a) buret reading will equal the percentage of Na 2O, (b) three times the buret
reading will equal the percentage of Na 2O, (c) every 3 mL will represent 1% Na2O (d) each
mL will represent 3% Na2O (e) the buret reading and the percentage of Na2O will be in the
respective ratio 2:3?
DOUBLE INDICATOR TITRATIONS
- The fact that certain indicators change color at different stages of a

neutralization is sometimes made use of in volumetric work to determine the
proportions of the components of certain mixtures by observing two endpoints in
a single titration.
A practical application of the principle of a double indicator titration is in the

analysis of mixtures containing Na2CO3 and NaOH or Na2CO3 and NaHCO3.
The change of color of phenolphthalein is not sharp at the point of formation
of bicarbonate; hence, the precision of these double indicator titrations is not
great as in most alkalimetric titrations, but by keeping the solution ice-cold,
three significant accuracy can be obtained. The use of creso red plus thymol

blue in place of phenolphthalein, together with the use of bromphenol blue
in place of methyl orange gives greater precision.
Case 1: NaOH + Na2CO3 + inert matter

- Consider the case of a mixture containing Na2CO3 and NaOH ( and inert
matter). The titration with standard acid , using phenolphthalein , would give a
color change of pink to colorless only when the NaOH had been neutralized and
the Na2CO3 has been half-neutralized(i.e., converted to NaHCO3). Methyl
orange would give a yellow color to the solution, and the additional volume of
acid required to change the color to pink would be that required to complete
the reaction with NaHCO3
- Additional volume of acid required for methyl orange end point is less than
volume required for phenolphthalein end point
NaOH
HCl A, mL A + B mL - phenolphthalein endpt

changes color(pink to colorless)
NaCl + H2O Na2CO3
* NaOH- neutralized
HCl B, mL Na2CO3 – half neutralized
NaHCO3
HCl B, mL
Methyl orange end pt
CO2 + NaCl (yellow color to pink) to complete
reaction
Case 2: Na2CO3 + NaHCO3 + inert matter

- The titration with standard acid, using phenolphthalein , would produce a color
change of pink to colorless when the Na2CO3 had been converted to NaHCO3.
Methyl orange would give a yellow color to the solution, and the additional
volume of acid required to change the color of the methyl orange would be
that required to complete the reaction with the NaHCO 3 formed from the
Na2CO3, plus that required to react with the original NaHCO 3.
- _ Additional volume of acid required for methyl orange end point is greater
than volume required for phenolphthalein end point

Na2CO3 - phenolphthalein endpt
HCl A, mL when Na2CO3 is converted to NaHCO3
NaHCO3
A, mL A+B * A = original vol

B = addtl vol of acid
CO2 NaHCO3
HCl B, mL

reaction
ex. A sample consisting of Na2CO3, NaOH and inert matter weighs 1.179 g. It is titrated with
0.300 N HCl with phenolphthalein as the indicator, and the solution becomes colorless after
the addition of 48.16 mL. methyl orange is then added and 24.08 mL more of the acid are
needed for the color change. What is the percentage NaOH and Na 2CO3?
NaOH
HCl 48.16 mL -24.08 mL - phenolphthalein endpt

NaCl + H2O Na2CO3 48.16
* NaOH- neutralized
HCl 24.08 mL Na2CO3 – half neutralized
NaHCO3
HCl 24.08 mL
reaction
Soln:
If the acid is added slowly, the stronger base (NaOH) is neutralized first. After
this reaction is complete, the Na2CO3 is converted to NaHCO3, at which the
phenolphthalein changes color. All this requires 30.00 mL of the acid. Since
the further reaction with the bicarbonate formed requires 5.00 mL of the acid,
of the total 35.00 mL used, 10.00 mL must have reacted with Na2CO3 , and
therefore, 25. 00 mL with the NaOH

𝑚𝑒𝑞 𝑁𝑎𝑂𝐻 = 𝑚𝑒𝑞 𝐻𝐶𝑙
𝑊𝑁𝑎𝑂𝐻
= 𝑁𝐻𝐶𝑙 × 𝑉𝐻𝐶𝑙
𝑀𝑊
𝑓 × 1000
𝑵𝑯𝑪𝒍 ×𝑽𝑯𝑪𝒍 × 𝑴𝑾𝑵𝒂𝑶𝑯

𝑾𝑵𝒂𝑶𝑯 =
𝒇𝑵𝒂𝑶𝑯 × 𝟏𝟎𝟎𝟎
𝒈
(𝟎. 𝟑 𝑵)(𝟐𝟒. 𝟎𝟖 𝒎𝑳) (𝟒𝟎 )
𝑾𝑵𝒂𝑶𝑯 = 𝒎𝒐𝒍
𝒆𝒒
𝟏 × 𝟏𝟎𝟎𝟎
𝒎𝒐𝒍
𝑾𝑵𝒂𝑶𝑯 = 𝟎. 𝟐𝟖𝟗 𝒈
𝑾𝑵𝒂𝑶𝑯
% 𝑵𝒂𝑶𝑯 = × 𝟏𝟎𝟎
𝑾𝒔𝒂𝒎𝒑𝒍𝒆
𝟎. 𝟐𝟖𝟗 𝒈
% 𝑵𝒂𝑶𝑯 = × 𝟏𝟎𝟎 = 𝟐𝟒. 𝟓𝟏%
𝟏. 𝟏𝟕𝟗 𝒈
𝑚𝑒𝑞 𝑁𝑎2 𝐶𝑂3 = 𝑚𝑒𝑞 𝐻𝐶𝑙
𝑊𝑁𝑎2 𝐶𝑂3
𝑀𝑊
𝑓 × 1000
𝑵𝑯𝑪𝒍 × 𝑽𝑯𝑪𝒍 × 𝑴𝑾𝑵𝒂𝟐 𝑪𝑶𝟑

𝑾𝑵𝒂𝟐 𝑪𝑶𝟑 =
𝒇𝑵𝒂𝟐 𝑪𝑶𝟑 × 𝟏𝟎𝟎𝟎
𝒈
(𝟎. 𝟑 𝑵)(𝟒𝟖. 𝟏𝟔. 𝒎𝑳) (𝟏𝟎𝟓. 𝟗𝟗 )
𝑾𝑵𝒂𝟐 𝑪𝑶𝟑 = 𝒎𝒐𝒍
𝒆𝒒
𝟐 × 𝟏𝟎𝟎𝟎
𝒎𝒐𝒍
𝑾𝑵𝒂𝟐 𝑪𝑶𝟑 = 𝟎. 𝟕𝟔𝟓𝟕 𝒈
𝑾𝑵𝒂𝟐 𝑪𝑶𝟑
% 𝑵𝒂𝟐 𝑪𝑶𝟑 = × 𝟏𝟎𝟎
𝟎. 𝟕𝟔𝟓𝟕 𝒈
% 𝑵𝒂𝟐 𝑪𝑶𝟑 = × 𝟏𝟎𝟎 = 𝟔𝟒. 𝟗𝟒%
𝟏. 𝟏𝟕𝟗 𝒈

Ex.2 A 1.200 g sample containing Na2CO3 and NaHCO3 and inert impurities is titrated cold
with 0.500N HCl with phenolphthalein as the indicator the solution turns colorless after the
addition of 15.0 mL of the acid . Methyl orange is then added and 22.mL more of the acid
are required to change the color of this indicator. What is the percentage Na 2CO3 and
NaHCO3 ?
Given:
Na2CO3 - phenolphthalein endpt
HCl 15, mL when Na2CO3 is converted to NaHCO3
NaHCO3
15, mL
22 mL
CO2 NaHCO3
HCl 22-15 mL

reaction
Reqd; a. % Na2CO3
b. % NaHCO3
Soln:
Na2CO3 is first converted to NaHCO3, requiring 15.00 mL of the acid. Of the
22.0 mL of additional acid added, 15.00 mL must have been required to
complete the reaction with this NaHCO3 formed and 7.00mL to react with the
NaHCO3 originally present
a. 𝑚𝑒𝑞 𝑁𝑎2 𝐶𝑂3 = 𝑚𝑒𝑞 𝐻𝐶𝑙
𝑊𝑁𝑎2 𝐶𝑂3
𝑀𝑊
𝑓 × 1000
𝑵𝑯𝑪𝒍 × 𝑽𝑯𝑪𝒍 ×𝑴𝑾𝑵𝒂𝟐 𝑪𝑶𝟑

𝑾𝑵𝒂𝟐 𝑪𝑶𝟑 =
𝒇𝑵𝒂𝟐 𝑪𝑶𝟑 × 𝟏𝟎𝟎𝟎
𝒈
(𝟎. 𝟓 𝑵)(𝟏𝟓 + 𝟏𝟓 𝒎𝑳) (𝟏𝟎𝟓. 𝟗𝟗 )
𝑾𝑵𝒂𝟐 𝑪𝑶𝟑 = 𝒎𝒐𝒍
𝒆𝒒
𝟐 × 𝟏𝟎𝟎𝟎
𝒎𝒐𝒍
𝑾𝑵𝒂𝟐 𝑪𝑶𝟑 = 𝟎. 𝟕𝟗𝟒𝟗 𝒈

𝑾𝑵𝒂𝟐 𝑪𝑶𝟑
% 𝑵𝒂𝟐 𝑪𝑶𝟑 = × 𝟏𝟎𝟎
𝟎. 𝟕𝟗𝟒𝟗 𝒈
% 𝑵𝒂𝟐 𝑪𝑶𝟑 = × 𝟏𝟎𝟎 = 𝟔𝟔. 𝟐𝟒𝟏𝟕%
𝟏. 𝟐 𝒈
b.
𝑚𝑒𝑞 𝑁𝑎𝐻𝐶𝑂3 = 𝑚𝑒𝑞 𝐻𝐶𝑙
𝑊𝑁𝑎𝐻𝐶𝑂3
𝑀𝑊
𝑓 × 1000
𝑵𝑯𝑪𝒍 × 𝑽𝑯𝑪𝒍 ×𝑴𝑾𝑵𝒂𝑯𝑪𝑶𝟑

𝑾𝑵𝒂𝑯𝑪𝑶𝟑 =
𝒇𝑵𝒂𝑶𝑯 × 𝟏𝟎𝟎𝟎
𝒈
(𝟎. 𝟓𝑵)(𝟐𝟐 − 𝟏𝟓 𝒎𝑳) (𝟖𝟒. 𝟎𝟏 )
𝑾𝑵𝒂𝑯𝑪𝑶𝟑 = 𝒎𝒐𝒍
𝒆𝒒
𝟏 × 𝟏𝟎𝟎𝟎
𝒎𝒐𝒍
𝑾𝑵𝒂𝑯𝑪𝑶𝟑 = 𝟎. 𝟐𝟗𝟒𝟎 𝒈
𝑾𝑵𝒂𝑯𝑪𝑶𝟑
% 𝑵𝒂𝑯𝑪𝑶𝟑 = × 𝟏𝟎𝟎
𝟎. 𝟐𝟗𝟒𝟎 𝒈
% 𝑵𝒂𝑯𝑪𝑶 𝟑 = × 𝟏𝟎𝟎 = 𝟐𝟒. 𝟓𝟎𝟐𝟗 %
𝟏. 𝟐 𝒈
Determination of the Proportion in which Components are present in a mixture:
Example: If 0.5000 g of a mixture of CaCO3 and BaCO3 requires 30.00 mL of a 0.2500N HCl
for neutralization, What is the percentage of each component?
let x = g CaCO3 and y = g BaCO3

x + y = 0.5000 equation1
eq of CaCO3 present = x = x .
CaCO3/2 50.04
eq of BaCO3 present = y = y .
BaCO3/2 98.69

eq CaCO3 + eq BaCO3 = eq HCl
x + y = 30.0 mL (0.250eq/L)
50.04 98.69 (1000mL/L)
equation2
Solving equations 1 and 2 simultaneously:
x = 0.247 g
y = 0.253 g
% CaCO3 = (0.247 / 0.500) x 100 = 49.4%
% BaCO3 = (0.253 / 0.500) x 100 = 50.6%
Example: The weight of combined LiOH, KOH and Ba(OH)2 in a mixture is 0.5000 g and
requires 25.43 mL of 0.500N acid for neutralization. The same weight of sample with CO 2
gives a precipitate of BaCO3 that requires 5.27 mL of the above acid for neutralization. Find
the weights of LiOH, KOH and Ba(OH)2 in the original mixture.
Let x = g LiOH and y = g KOH and z = g Ba(OH)2
x + y + z = 0.5000 1
eq LiOH = x eq Ba(OH)2 = z .
23.95/1 171.36/2
eq KOH = y .
56.11/1
eq LiOH + eq KOH + eq Ba(OH)2 = 25.43mL(0.5eq/L)
1000mL/L
equation 2
eq Ba(OH)2 = eq BaCO3 = 5.27 mL (0.5 eq/L)
1000mL/L
wt Ba(OH)2 x 2 eq/mol = 2.635 x 10-3 eq
171.36 g/mol
wt Ba(OH)2 = 0.2258 g
x + y + 0.2258 = 0.5000 1
x + y = 0.2742
eq LiOH + eq KOH + eq Ba(OH)2 = 25.43mL(0.5eq/L)
1000mL/L
equation 2
eq LiOH + eq KOH + 2.635 x 10-3 eq = 0.012715 eq
x + y = 0.01008
23.95/1 56.11/1
Solving equations 1 and 2 simultaneously:
x = 0.217 g
y = 0.0572 g
Assignment:
21- A mixture consisting entirely of Li2CO3 + BaCO3 weighs 1.000 g and requires 15.00 mL of
1.000 N HCl for neutralization. Find the percentage of BaCO 3 and of combined Li in the
sample.
22- A mixture of pure BaCO3 and pure Na2CO3 weighs 1.000 g and has the total neutralizing
power of 15.37 meq of CaCO3. Calculate the percentage of combined CO2 in the mixture
and the weight of Li2CO3 that has the same neutralizing power as 1.000 g of the above
mixture.

MODULE 6: VOLUMETRIC METHODS OF ANALYSIS:UNIT 3: REDOX TITRATION
QUANTITATIVE ANALYSIS -
REDOX
•Volumetric Analysis
Divisions:
1- Neutralization methods – acidimetry (acid determination) and alkalimetry (alkali
determination)
2- Oxidation and Reduction – “redox” – oxidimetry and reductimetry
3- Precipitation methods – precipitimetry
4- Complex ion formation methods - compleximetry
Volumetric Analysis is more commonly as

TITRATION
REDOX TITRATION
Redox titration is a division of volumetric analysis where the reactants are oxidizing
reducing agents
Oxidation - refers to a reaction in which an element increases in oxidation state due to
loss of electrons
– loss of electrons
- oxidation state tends to move to the positive side
oxidation numbers
– 8 … – 3 – 2 – 1 0 +1 +2 + 3 … + 8
substances that undergo these type of change in oxidation state are called reducing
agents
example: Mn+2 Mn+7
Mn is a reducing agent and is capable of being oxidized to Mn +7
+2

Reduction - refers to a reaction in which an element decreases in oxidation state due to
gain of electrons
– gain of electrons
- oxidation state tends to move to the negative side
oxidation numbers
– 8 … – 3 – 2 – 1 0 +1 +2 + 3 … + 8
substances that undergo these type of change in oxidation state are called oxidizing
agents
example: S+6 S–2

S+6 is an oxidizing agent and is capable of being reduced to S–2
Example: H+ + e- H0
H+ is an oxidizing agent and is capable of being reduced to hydrogen
Zn + 2H+ Zn2+ + H2
free Hydrogen is a reducing agent and is capable of being oxidized to hydrogen

ion
Zinc ion is an oxidizing agent and is capable of being reduced to a zinc metal
Oxidizing agent - substance that decrease in oxidation number

- substance responsible for oxidation
- particles which accepts electrons
Reducing agent - substance that increase in oxidation number

- substance responsible for reduction
- Particles which donates electrons
Solutions used in titrations:

Oxidizing agents Reducing agents
K2Cr2O7 FeSO4
KMnO4 FeSO4.(NH4)2SO4.6H2O
K3Fe(CN)6 H2C2O4
I2 Na2C2O4
Ce(SO4)2 Na2S2O3
KIO3 SnCl2
KBrO3 Na3AsO3
Important Combinations of Oxidizing Agent and Reducing Agent in Redox Titrations:
1. K2Cr2O7 and ferrous solutions

2. KMnO4 and ferrous solutions
3. KMnO4 and Na2C2O4
4. I 2 and Na2S2O3
5. Hypochlorites (ex. HClO4) and arsenious acid
OXIDATION - REDUCTION EQUIVALENTS

g-equiv wt of O.A. AND R.A. = FW / tot. change in O.S of its constant element
= FW / f
Ex. Mn +7 → Mn +2
g-equiv wt = KMnO4
5
How many grams of the following reducing substances constitute the gram equivalent
weight in each case:
(a) FeSO4.7 H2O
(b) SnCl2
(c) H2C2O4.2H2O (oxalic acid)
(d) KHC2O4.H2O (potassium binoxalate)
(e) KHC2O4.H2C2O4.2H2O (potassium tetroxalate)
(f) H2S (oxidized to S)
(g) H2S (oxidized to H2SO4)
(h) Na2S2O3.5H2O (oxidized to Na2S4O6)
(i) H2O2
reducing substances – oxidation process takes place

(a) FeSO4.7 H2O
Fe2+ (+2) Fe3+ (+3) + e- f=1
eq wt = FeSO4.7 H2O g/mol = 278 grams/eq
1 eq/mol
(b) SnCl2
Sn2+ (+2) Sn4+ (+4) + 2e- f=2
eq wt = SnCl2 g/mol = 94.8 grams/eq
2 eq/mol
(c) H2C2O4.2H2O
C2O42- (C+3) 2CO2 (C+4) + 2e- f=2
eq wt = H2C2O4.2H2O g/mol = 63.03 grams/eq
2 eq/mol
(d) KHC2O4.H2O
C2O42- (C+3) 2CO2 (C+4) + 2e- f=2
eq wt = KHC2O4.2H2O g/mol = 73.07 grams/eq
2 eq/mol
(e) KHC2O4.H2C2O4.2H2O
2C2O4-2 4CO2 + 4e- f=4
eq wt = KHC2O4.H2C2O4.2H2O g/mol = 63.55 g/eq
4 eq/mol

(f) H2S (oxidized to S)
S2- (–2) S0 (0) + 2e- f=2
eq wt = H2S g/mol = 17.04 grams/eq
2 eq/mol
(g) H2S (oxidized to H2SO4)
S2- (–2) S6+ (+6) + 8e- f=8
eq wt = H2S g/mol = 4.26 grams/eq
8 eq/mol
(h) Na2S2O3.5H2O (oxidized to Na2S4O6)
2S2O32- (+ 2) S4O62- (+2.5) + 1e- f=1
eq wt = Na2S2O3.5H2O g/mol = 248.2 g/eq
1 eq/mol
(i) H2O2 (as a reducing agent, oxidizes to free O)
H2O2 (–1) O20 (0) + 2e- f=2
eq wt = H2O2 g/mol = 17.01 g/eq
2 eq/mol
How many grams of the following oxidizing substances constitute the gram equivalent
weight in each case:
(a) K3Fe(CN)6 (d) I2
(b) KMnO4 (e) K2Cr2O7
(c) KBrO3 (reduced to bromide) (f) H2O2
oxidizing substances – reduction process takes place

(a) K3Fe(CN)6
Fe(CN)63- (Fe+3) + 1e- Fe(CN)64- (Fe+2) f = 1
eq wt = K3Fe(CN)6 g/mol = 0.3293 g/eq
1 eq/mol
(b) KMnO4
** when reduced in the presence of an acid, permanganate forms manganous ions
MnO4–1 (+7) + 5e- Mn2+ (+2) f = 5

eq wt = KMnO4 g/mol = 31.61 g/eq
5 eq/mol
** in alkaline solution, permanganate is reduced to MnO2

MnO4–1 (+7) + 3e- Mn2+ (+4) f=3
eq wt = KMnO4 g/mol = 52.68 g/eq
3 eq/mol
(c) KBrO3 (reduced to bromide)

KBrO3 (+5) + 6e- Br- (–1) f=6
eq wt = KBrO3 g/mol = 27.84 g/eq
6 eq/mol
(d) I2
I2 (0) + 2e- 2I- (–1) f=2

eq wt = I2 g/mol = 126.9 g/eq
2 eq/mol
(e) K2Cr2O7
Cr2O72- (+6) + 6e- 2Cr3+ (+3) f=6
eq wt = K2Cr2O7 g/mol = 49.03 g/eq
6 eq/mol
(f) H2O2 (as an oxidizing agent, reduce to H2O)

H2O2 (–1) + 2e- H2O (–2) f=2
eq wt = H2O2 g/mol = 17.01 g/eq
2 eq/mol
ASSIGNMENT
Exercises:
1. How to determine the factor of reducing agent and oxidizing agent:
a. Fe + HCl → FeCl3 + H2
b. HNO3 + H2S → S + NO + H2O
c. KMnO4 + LiCl + H2SO4 → Cl2 + MnSO4 + K2SO4 +Li2SO4 +H2O
d. K2Cr2O7 + KI + H3PO4 → I2 + CrPO4 + K3PO4 + H2O
e. K2Cr2O7 + FeSO4 + H2SO4 → Cr2(SO4)3 + Fe2(SO4)3 + K2SO4 + H2O
f. MnO4 - + Fe +2 + H+ → Mn++ + Fe3+ + H2O
g. MnO4 + C2O4 + H
- -2 + → Mn ++ + CO2 + H2O
2. What fraction of the formula weight of each of the ff compounds represents the
equivalent weight in a redox process in which the product formed is as indicated:
(a) Ce(SO4)2.2(NH4)2SO4.2H2O ( Ce3+)
(b) As2O5 ( As3+)
(c) KIO3 ( ICl32-)
(d) Na2SeO4 ( SeO32-)
(e) VOSO4 ( VO3-)
Mo2O3 ( H2MoO4
REDOX:OXIDATION- REDUCTION
OXIDATION - REDUCTION EQUIVALENTS
g-equiv wt of O.A. AND R.A.

= FW or MW / tot. change in O.S of its constant element
𝐹𝑊
𝑔 − 𝑒𝑞𝑢𝑖𝑣 𝑤𝑡 = 𝑡𝑜𝑡 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑂.𝑆
Where: FW = formula weight

MW = molecular weight
O.S = oxidation state/number
Ex. Mn +7 → Mn +2
g-equiv wt = KMnO4
5
Fe +2 → Fe +3
f =1
g-equiv wt = Fe
5
𝑵𝑹.𝑨 𝑵𝒂𝒄𝒊𝒅
=
𝒇𝑹.𝑨 𝒇𝒂𝒄𝒊𝒅
𝑵𝑶.𝑨 𝑵𝒂𝒄𝒊𝒅
=
𝒇𝑶.𝑨 𝒇𝒂𝒄𝒊𝒅
Example: How much water must be added to 50.0 mL of a solution of HNO 3which is 2N as
an acid to make the resulting solution 2.0N as an oxidizing agent? Assume
reduction of the HNO3 to NO
HNO3 to NO
𝑓𝐻𝑁𝑂3 = |5 − 2| = 3 × 1 = 3
=
𝒇𝑶.𝑨 × 𝑵𝒂𝒄𝒊𝒅
𝑵𝑶𝑨 =
𝒇𝒂𝒄𝒊𝒅
𝒆𝒒
𝟑 𝒎𝒐𝒍 × 𝟐𝑵
𝑵𝑶𝑨 = 𝒆𝒒 = 𝟔𝑵 𝒂𝒔 𝑶. 𝑨
𝟏𝒎𝒐𝒍
𝑉1 𝐶1 = 𝑉2 𝐶2
As Oxidizing agent ,O.A

𝑉1 = 50 𝑚𝐿 V2= ?
C1 = 6N C2 = 2N
50mL(6N) = V2 ( 2N)
V2 = 150 mL
𝑉𝐻2𝑂 = 150 − 50 = 100 𝑚𝐿

Example: From the following data , find the ratio of the Normality of the HNO 3 as an
oxidizing agent, to the normality of the tetroxalate as a reducing agent.
1.00 mL HNO3 ≎ 1.246 mL NaOH
1.00 mL NaOH ≎ 1.743 mL KHC2O4.H2 C2O4.2H2O
The NaOH is 0.1200 N ( oxalate oxidized to CO2; nitrate is reduced to NO)
Given:
1.00 mL HNO3 ≎ 1.246 mL NaOH
1.00 mL NaOH ≎ 1.743 mL KHC2O4.H2 C2O4.2H2O
N NaOH = 0.1200 N
Reqd:
Ratio of N HNO3 as O.A to N Ktet as R.A
Soln:
[𝑂]
𝐶2 𝑂4−2 → 𝐶𝑂2−2 𝑓 = 4 𝑎𝑙𝑤𝑎𝑦𝑠 𝑅. 𝐴
[𝑅]
𝑁𝑂3−1 → 𝑁𝑂 𝑓 = 3
𝑚𝑒𝑞𝐻𝑁𝑂3 𝑎𝑠 𝑎𝑐𝑖𝑑 = 𝑚𝑒𝑞𝑁𝑎𝑂𝐻 𝑎𝑠 𝑏𝑎𝑠𝑒

𝑁𝑎 𝑉𝑎 = 𝑁𝑏 𝑉𝑏
(0.1200𝑁) (1.246 𝑚𝐿)
𝑁𝐻𝑁𝑂3 = = 0.1495 𝑁 𝑎𝑠 𝑎𝑛 𝑎𝑐𝑖𝑑
1𝑚𝐿
N as O.A
=
𝒇𝑶.𝑨 × 𝑵𝒂𝒄𝒊𝒅
𝑵𝑶𝑨 = 𝒇𝒂𝒄𝒊𝒅
𝒆𝒒
𝟑 𝒎𝒐𝒍 × 𝟎.𝟏𝟒𝟗𝟓𝑵
𝑵𝑶𝑨 = 𝒆𝒒 = 𝟎. 𝟒𝟒𝟖𝟓𝑵 𝒂𝒔 𝑶. 𝑨
𝟏
𝒎𝒐𝒍
𝑚𝑒𝑞𝑁𝑎𝑂𝐻 𝑎𝑠 𝑏𝑎𝑠𝑒 = 𝑚𝑒𝑞𝐾𝑡𝑒𝑡 𝑎𝑠 𝑎𝑐𝑖𝑑
Note: base is always base
𝑁𝑏 𝑉𝑏 = 𝑁𝑎 𝑉𝑎
(0.1200𝑁) (1.0 𝑚𝐿)
𝑁𝐾𝑡𝑒𝑡 = = 0.0688 𝑁 𝑎𝑠 𝑎𝑛 𝑎𝑐𝑖𝑑
1.743 𝑚𝐿
𝑵𝑹.𝑨 𝑵𝒂𝒄𝒊𝒅
=
𝒇𝑹.𝑨 𝒇𝒂𝒄𝒊𝒅
𝒇𝑹.𝑨 × 𝑵𝒂𝒄𝒊𝒅
𝑵𝑹𝑨 = 𝒇𝒂𝒄𝒊𝒅

𝒆𝒒
𝟒 𝒎𝒐𝒍 × 𝟎.𝟎𝟔𝟖𝟖𝑵
𝑵𝑹𝑨 = 𝒆𝒒 = 𝟎. 𝟎𝟗𝟏𝟖 𝒂𝒔 𝑹. 𝑨
𝟑𝒎𝒐𝒍
𝑵𝑯𝑵𝑶𝟑 𝒂𝒔 𝑶.𝑨 𝟎. 𝟒𝟒𝟖𝟓 𝑵

𝑹𝒂𝒕𝒊𝒐 = = = 𝟒. 𝟖𝟖𝟔
𝑵𝑲𝒕𝒆𝒕 𝒂𝒔 𝑹.𝑨 𝟎. 𝟎𝟗𝟏𝟖 𝑵
Example: a ferrous solution contains 1.176 g of FeSO4.(NH4)2 SO4.6H2O in 30.00 ml; a

dichromate solution contains 0.2940 g of K2Cr2O7 in 20.00 mL. Find (a) the normality of the
ferrous solution as a reducing agent, (b) the normality of the dichromate solution as an
oxidizing agent, (c) the volume of the dichromate equivalent to 1.000 mL of the ferrous
soln.
NFeSO4.(NH4)2SO4.6H2O = (1.176 g)1 eq/mol(1000 mL/L)
(392.14 g/mol)(30.00 mL)
= 0.09996 N
NK2Cr2O7 = (0.2940 g)6 eq/mol(1000 mL/L) = 0.2998 N
(294.19 g/mol)(20.00 mL)
eqFeSO4.(NH4)2SO4.6H2O = eqK2Cr2O7
(0.09996N)(1.000 mL) = (0.2998N)(V K2Cr2O7)
VK2Cr2O7 = 0.3334 mL
ASSIGNMENT:
3. How many grams per milliliter does a soln of KNO2 contain if it is 0.100 N as a
reducing agent?How many grams of SO2 is contained in a liter of a solution of
H2SO3 which is 0.05860 N as a reducing agent?
4. What is the normality of a nitric acid solution to be used as an oxidizing agent
(reduced to NO) if it contains 55.50% by weight of HNO 3and has a specific
gravity of 1.350
5. In the reaction expressed by the equation: 13Pb 3O4(s) + 2Mn3O4(s) + 72H +
6MnO4- + 39Pb2+ + 36H2O (a) What is the numerical value of the equivalent
weight of Pb3O4 as an oxidizing agent (b) the milliequivalent weight of Mn 3O4
as a reducing agent, and (c) the volume of 0.1500 N FeSO 4 solution required
to titrate the permanganate formed from 0.2000 mmol of Mn 3O4?
PERMANGANATE PROCESS
KMnO4 – used extensively as an oxidimetric standard – serves as its own indicator

3 ways to use KMnO4 solution:
1- it is used in the presence of acid in the direct titration of a number or oxidizable cations
and anions:
Substance Oxidized to Substance Oxidized to
Fe 2+ Fe 3+ H2O2 O2
Sn2+ Sn4+ Mo3+ MoO32–
VO2+ VO3– Ti3+ TiO2+

C2O42– CO2 U4+ UO22+
NO2 – NO3 – As 3+ AsO43–
SO3 2– SO4 2–
2- it is used in the presence of acid in the direct titration of a number of reducible

substances ( a measured amount of
reducing agent (ferrous salt or oxalate) is added and after reduction is complete, the
excess reducing agent is titrated with standard permanganate)
Substance Reduced to
MnO4 – Mn2+
Cr2O72 – Cr3+
MnO2, Mn3O4 Mn2+
PbO2, Pb2O3, Pb3O4 Pb2+
Ce 4+ Ce 3+
3- it is used in neutral or alkaline solution in the titration of few substances. In these case
permanganate is reduced to MnO2, w/c precipitates. The MnO4 – has an
oxidizing power 3/5 of what it has in the presence of acid
Substance Oxidized to
Mn 2+ MnO2
HCOOH (formic acid) CO2
Example: What is the N of a solution of potassium permanganate if 40.00 mL will oxidize that
weight of potassium tetroxalate, KHC2O4.H2C2O4.2H2O, which requires 30.00 mL of 0.5000 N
sodium hydroxide solution for its neutralization, and what is the value of 1.000 mL of the
KMnO4 in terms of grams As2O3 in the titration of As3+ to H3AsO4 in the presence of acid?
Neutralization process: eq tetroxalate = eq NaOH

weightKHC2O4.H2C2O4.2H2O x factortetrox = NNaOH VNaOH
MWtetrox
weightKHC2O4.H2C2O4.2H2O = 0.50N(30 mL) x 254.2 g/mol
3 eq/mol
weightKHC2O4.H2C2O4.2H2O = 1271 g
Redox process: eq tetroxalate = eq KMnO4 weightKHC2O4.H2C2O4.2H2O(factortetro)= NKMnO4VKMnO4
MWtetrox
1271 g (4 eq/mol ) = NKMnO4(40mL)
254.2 g/mol
NKMnO4 = 0.500 N
eq KMnO4 = eq As2O3
0.500 N(1.000mL) = weight As2O3 (4 eq/mol )
1000mL/L 197.84g/mol
weight As2O3 = 0.02473 g As2O3
Example: What is the percentage of iron in a sample of iron ore weighing 0.7100 g if, after
solution and reduction of the iron with amalgamated zinc, 48.06 mL of KMnO 4 (1.000 mL ≈
0.006700 g Na2C2O4) is required to oxidize the iron? How many grams of KMnO 4 are
contained in each milliliter of the solution?

eq KMnO4 = eq Na2C2O4
NKMnO4 (1.00 mL) = 0.006700 g Na2C2O4 (2 eq/mol )
1000mL/L 134 g/mol
NKMnO4 = 0.100 N
eq KMnO4 = eq Fe
0.100N(48.06 mL) = weight Fe (1 eq/mol )

1000mL/L 55.85 g/mol
weight Fe = 0.2684 g % Fe = 0.2684/0.71 = 37.80%
each mL of normal KMnO4 contains KMnO4

5000
wt KMnO4 = (0.100 eq)(158.04 g/mol)( 1 L ) = 0.003161 g
mL L 5 eq/mol 1000mL Ml
Example: How many grams of H2O2 are contained in a solution that requires for titration
14.05 mL of KMnO4 of which 1.000 mL ≈ 0.008378 g Fe (i.e., will oxidize that amount of iron
from the divalent to the trivalent state)? How many g and how many mL of oxygen
measured dry and under standard conditions are evolved during the titration?
eq KMnO4 = eq Fe
NKMnO4 (1.000 mL ) = 0.008378 g Fe (1 eq/mol )

1000mL/L 55.85g/mol
NKMnO4 = 0.1500 N
eq KMnO4 = eq H2O2
0.1500N( 14.05 mL ) = weight H2O2 (2 eq/mol )
1000mL/L 34.02g/mol
weight H2O2 = 0.03585 g H2O2
eq KMnO4 = eq O2
0.1500N( 14.05 mL ) = weight O2 (2 eq/mol )
1000mL/L 32g/mol
weight O2 = 0.03372 g O2
At STP, 1mol O2 occupies 22.4 L

volume O2 = 0.03372 g O2 (1.00 mol)(22400mL)
32 g 1 mol
= 23.60 mL
Example: What is the percentage of MnO2 in a pyrolusite ore if a sample weighing 0.4000 g
is treated with 0.6000 g of pure H2C2O4.2H2O and dilute H2SO4 and after reduction has
taken place (MnO2 + H2C2O4 + 2H+ Mn2+ + 2CO2 + 2H2O), the excess oxalic acid requires
26.26 mL of 0.1000 N KMnO4 for titration? If pure As2O3 were used instead of oxalic acid,

how many grams would be required in order for the other numerical data to remain the
same?
eq MnO2 = eq H2C2O4.2H2O – eq KMnO4

wt MnO2 (2 eq/mol ) =
86.94g/mol
0.600g(2eq/mol) – 26.26mL(0.1N)
126.07 g/mol 1000mL/L
weight MnO2 = 0.2996 g % MnO2 = 0.2996/0.4 = 74.9%
eq As2O3 = eq H2C2O4.2H2O
weight As2O3 ( 4 eq/mol ) = 0.600g(2eq/mol)
197.84 g/mol 126.07 g/mol
weight As2O3 = 0.4708 g
Example: What is the milliequivalent weight of Pb 3O4 and of Pb in the calculation analysis of
red lead (impure Pb3O4) Pb3O4(s) + H2C2O4 + 3SO42- + 6H+ 3Pb2+ + CO2 + 4H2O
meq wt Pb3O4 = Pb3O4 mg/mmol = 0.3428

2000 meq/mmol
meq wt Pb = 3Pb mg/mmol = 0.3108

2000 meq/mmol
Example: A steel containing 0.90% Mn is analyzed by the three standard methods:
Bismuthate, Chlorate (Williams)and Volhard, in each case with a 2.50 g sample, 0.0833 N
KMnO4 and 0.100 N FeSO4 solutions. Calculate the volume of KMnO4 required in each case.
Bismuthate Method: Mn is oxidized to KMnO4, and after reduction with 25.0 mL of standard
FeSO4 (MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O) the excess ferrous ion is titrated
with the standard KMnO4
eq Mn = eq FeSO4 – eq KMnO4
wt Mn x 5 eq/mol = 0.100N(25.0 mL) – 0.0833NVKMnO4
54.94g/mol 1000mL/L 1000mL/L
Weight Mn = 0.90% (2.50 g) = 0.0225 g

100%
2.048 x 10-3 = 2.5 x 10-3 – 8.33 x 10-5 VKMnO4
VKMnO4 = 5.426 mL
Determination of Mn in carbon steel
Example: A steel containing 0.90% Mn is analyzed by the three standard methods:

Bismuthate, Chlorate (Williams)and Volhard, in each case with a 2.50 g
sample, 0.0833 N KMnO4 and 0.100 N FeSO4 solutions. Calculate the volume
of KMnO4 required in each case.

Bismuthate Method: Mn is oxidized to KMnO4, and after reduction with 25.0 mL of standard
FeSO4 (MnO4- + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O) the excess ferrous ion
is titrated with the standard KMnO4
meq Mn = meq FeSO4 – meq KMnO4

W = NxV - NxV
MW
f(1000)
W Mn = 0.100N(25.0 mL) – 0.0833N xVKMnO4

54.94 g/mol
5eq/mol(1000)
Weight Mn = 0.90% (2.50 g) = 0.0225 g

100%
2.048 = 2.5 – 8.33 x 10-2 VKMnO4
VKMnO4 = 5.426 mL
Chlorate Method: Mn is oxidized with KClO3 to MnO2, which is filtered and dissolved in 25.0
mL of the standard FeSO4 (MnO2 + 2Fe2+ + 4H+ Mn2+ + 2Fe3+ + 2H2O). The
excess acid is titrated with the standard KMnO4.
MnO2 (Mn+4) + 2e- Mn2+ (+2)

meq Mn = meq FeSO4 – meq KMnO4
W = NxV - NxV
MW
f(1000)
W Mn = 0.100N(25.0 mL) – 0.0833N xVKMnO4

54.94 g/mol
2eq/mol(1000)
Weight Mn = 0.90% (2.50 g) = 0.0225 g

100%
8.1908 x 10-1 = 2.5 – 8.33 x 10-2 VKMnO4
VKMnO4 = 20.18 mL = 20.2 mL
Volhard Method: Mn is titrated directly with KMnO4 in a solution kept neutral with ZnO
(3Mn2+ + 2MnO4- + 2ZnO 5MnO2 + 2Zn2+)
The oxidizing power of KMnO4 in neutral solution only three fifths (3/5) as great as it is in acid
solution
Mn2+ (+2) MnO2 (Mn+4) + 2e-
Mn (+2) + MnO4 (Mn+7) & MnO4-(Mn+7)
2+ - MnO2(Mn+4)

5 3
meq Mn = meq KMnO4
W = NxV
MW
f(1000)
W Mn = 0.0833Nacid (3/5) VKMnO4

54.94 g/mol
2eq/mol(1000)
Weight Mn = 0.90% (2.50 g) = 0.0225 g

100%
8.1908 x 10-1 = 4.998 x 10-2 VKMnO4
VKMnO4 = 16.388 mL = 16.4 mL
DICHROMATE AND CERIC PROCESSES
Dichromate and Processes are redox titrations where the oxidizing agents use are K2Cr2O7
and Ce(SO4)2, respectively. The most common reducing agents used in this
process are ferrous solutions
Advantages of Dichromate and Ceric Processes over Permanganate Process

- stable even at higher temperatures unlike permanganate which easily
decomposes
Disadvantages of Dichromate and Ceric Processes over Permanganate Process

-special indicator (known as redox indicator) is used in each case whereas
permanganate serves as its own indicator
- the sodium salt of diphenyl amine sulfonate is the most commonly used redox
indicator
whose change is from colorless to purple
Reactions:
K2Cr2O7 → Cr +3 factor of K2Cr2O7 = ( 6 -3)( 2) = 6
Cr2O7= → 2Cr+3
Ce(SO4)2 → Ce +3 factor of Ce(SO4)2 = ( 4 -3)(1) = 1
MnO4 -, Cr2O7=, Ce +3 : O.A

Fe + 2 → Fe in the presence of acid
+3
HCl
Applications of Dichromate/Ceric Process

1. Determination of Fe in Limonite in solutions containing Fe like FeCl 3 solution
2. Determination of Cr in Chromite, an ore whose composition is Fe(CrO2)2
Example:
1. In the standardization of a K2Cr2O7 solution against 99.85% pure Fe wire , 42.42
mL of the dichromate were added to the HCl solution of the wire. The wt of
the wire was 0.2200 g and 3.27 mL of FeSO4 soln ( 0.1011 N as reducing agent)
were required to complete the titration. Calculate the normality of the
dichromate as an oxidizing agent
me Fe = me K2Cr2O7 (O.A) – me FeSO4 (R.A)
W = NxV - NxV
MW
f(1000)
(0.2200 g)(0.9985) = (42.42 mL)(N K2Cr2O7) – (3.27mL x 0.1011 N)

55.85 g/mol
1eq/mol(1000)
N K2Cr2O7 = 0.1005 N
2. A sample of chromite contains 30.00% Cr 2O3. After fusion of a 0.200-g sample of

Na2O2 and dissolving in acid, how many grams of FeSO4.(NH4)2SO4.6H2O should be
added so that the excess ferrous ions will require 15.00 mL of a solution of K2Cr2O7
containing 0.200 millimole of Cr millilitre?

me Cr2O3 = me FAS - me K2Cr2O7
(0.3)(0.2 g) = W FAS -(15mL)(0.2 mmol/mL)(3 me/mol)

152 g/mol 392 g/mol
6(1000) 1 (1000)
WFAS = 4.458 g
3. In the analysis of a sample of limonite by titrating with a solution of K 2Cr2O7 of which 1.00
mL ≎ 0.01117 g Fe. What wt of sample should be taken so that the percentage of Fe 2O3
will be found by multiplying the buret reading by 4? How many grams of K 2Cr2O7 are in
each millilitre of the above dichromate?
a. me K2Cr2O7 = me Fe
(N K2Cr2O7)(1 mL) = 0.01117g
-----------
55.85 g/mol
-------------
(1eq/mol)(1000)
N K2Cr2O7 = 0.2N
b. me Fe2O3 = me K2Cr2O7
% Fe2O3 = N K2Cr2O7 x V K2Cr2O7 x me wt Fe2O3 x 100

W spl
4 V K2Cr2O7 = ( 0.2 N)( V K2Cr2O7 )(159.7 g/mol)

W spl x 2 eq/mol x 1000
W sample = 0.3992 g
c. N K2Cr2O7 = W x f
MW x V
W K2Cr2O7 = (0.2 eq/mol)(294.7 g/mol)(1ml/1000)

6 eq/mol
W K2Cr2O7 = 0.009807 g
4. A 0.500 g sample of chromite is fused with Na2O2 leached with water, and acidified.
The Cr is reduced by adding 2.78 g of FeSO4.7H2O crystals. The excess ferrous ions

then then require 10.0 mL K2Cr2O7 for oxidation , and 1.00mL K2Cr2O7 ≎ 0.1060 g
Fe2O3. What is the percentage of Cr in the chromite?
me K2Cr2O7 = me Fe2O3
(1mL)( N K2Cr2O7 ) = 0.0160 g

156.7 g/mol
2(1000)
N K2Cr2O7 = 0.2 N
me Cr = me FeSO4.7H2O - me K2Cr2O7
WCr = 2.78 g - (10mL)(0.2N)

52 g/mol 278.02g/mol
3(1000) 1(1000)
W Cr = 0.1387 g
% Cr = 0.1387 g x 100
0.5 g
OR:
% Cr = (me FeSO4.7H2O - me K2Cr2O7) x me wt Cr x 100
W sample
% Cr = 2.78 - (10mL)(0.2N) 52
278.02/1(1000) 3(1000)
X 100
0.5 g
% Cr = 27.7%
ASSIGNMENT:
16. What is the percentage of Fe2O3 in a sample of limonite ore if the iron from a
0.5000 g sample is reduced and titrated with 35.15 mL of K2Cr2O7 solution of
which 15.00 mL is equivalent in oxidizing power to 25.00 mL of KMnO 4 solution
which has an “iron value” of 0.004750 g?
-17. A solution contains 2.608 g KMnO4 per 750 mL. (a) What is the normality as an
oxidizing agent? And what is the value of each mL in terms of g of (b)
FeSO4.(NH4)2SO4.6H2O, (c) As2O3, (d) KHC2O4, (e) H2O2 and (f) U(SO4)2
(oxidized to UO22+)?
18. - A sample of pyrolusite weighing 0.6000 g is dissolved in a solution containing 5.00
mL of 6.00 N H2SO4 and 0.900 g of H2C2O4.2H2O. The excess oxalate then requires
24.00 mL of KMnO4 solution for titration. If each mL of the KMnO4 will oxidize the Fe(II)
in 0.03058 g FeSO4.7H2O, what is the oxidizing power of the sample in terms of MnO2?
84.33%

IODIMETRY
Iodimetry is the redox titration of iodine ( as an oxidizing agent) against sodium thiosulfate
with starch as the indicator. The end point color is deep blue
Reaction:
I2 + 2Na2S2O3 → 2NaI + Na2S4O6
Where:
Na2S2O3 is sodium thiosulfate
Na2S4O6 is sodium tetrathionate
The factor of I 2 = [ 0- (-1)][2] = 2

The factor of Na2S2O3 = [2.5-2][2] = 1
Applications of Iodimetry:
1. Analysis of Reducing Agents (such as H 2S, sulfites, arsenites, stannous salts)
Reducing Agent is directly titrated with I 2
me I 2 = me reducing agent
2. Analysis of Oxidizing agents ( such as permanganate, chromate, H 2O2)

The method makes use of the fact that all oxidizing agents oxidize iodide in dilute
acid solution to free iodine ( as I 2), which in turn can be titrated with standard
sodium thiosulfate
Oxidizing agent + excess KI free iodine in the form I 2 which in turn

is titrated with Na2S2O3
NaI + Na2S4O6
me oxidizing agent = me I 2 = me Na2S2O3
Note: When O.A are analyzed iodimetrically, it is important to titrate most of the
liberated iodine with the thiosulfate before adding the starch indicator.
Otherwise , so much of the blue-iodo starch compound is formed that the
thiosulfate reacts only very slowly with it
Standardization of Iodine:
Stoichiometry : H3AsO3 + I 2 + HCO3- H3AsO4 + 2I- + 2CO2 + H2O
As2O3 + 6OH- ⇔ 2 AsO3 -3 + 3H2O
me wt As2O3 =
MW As2O3
2(2X1000)
Antimony can be oxidized by iodine: Sb +3 → Sb+5

Standardization of Thiosulfate:
me wt KBrO3 = KBrO3 / 6(1000)

BrO3 - (+5) + 6e- → Br- (-1) f= 6
me wt KIO3 = KIO3 / 6 (1000)

IO3- (+5) + 6e- → I- (-1) f=6
me wt K2Cr2O7 = K2Cr2O7 /6(1000)

Cr2O7= + 6I- + 14H+ → 3I2 + 2 Cr+3 + 7H2O
me wt Cu = Cu / 1(1000)
2Cu++ + 4I- → 2 CuI + I2
Stoichiometry:
BrO3- + 6I- + 6H+ → Br- 3 I2 + 3H2O
IO3- + 5I - + 6H+ → 3 I2 + 3H2O
Cr2 O7= + 6I - + 14H+ → 2Cr+3 + 3 I 2 + 7H2O
2Cu++ + 4I - → 2CuI + I 2
1. What is the value in terms of grams of As2O3 of each milliliter of an I 2 soln of which 1.00
mL is equivalent to 0.0300 g of Na2S2O3 ?
a. me I 2 = me Na2S2O3
1mL(N I 2) = 0.03 g
158.11 g/mol
1 eq/mol(1000)
N I2 = 0.1897 N
b. me I 2 = me As2O3
1mL( 0.1897 N) = g As2O3

As+3 → As+5
197.84 g/mol
f = 5-3= 2x2 = 4
4eq/mol(1000)
W As2O3 = 0.009373 g
2. If 48.0 mL of a soln of thiosulfate are required to titrate the I 2 liberated from an excess of
KI by 0.300 g of KIO3 what is the normality of the thiosulfate and the value of
each milliliter of it in terms of grams of I2 ?

0.30 g KIO3 + x’s KI → I2 + Na2S2O3 → NaI
me S2O3= = me KIO3 KIO3 (+5) + 6e- → KI (-1)

f = +5 –(-1) = 6x1 = 6
48 mL(N S2O3= ) = 0.300 g

214.01 g/mol
6eq/mol(1000)
N S2O3= = 0.1752 N
me S2O3= = me I 2 I2 (0) +2e- →2 I- ( -1)

f = [0- (-1)] = 1x2 =2
(1mL)(0.1752N) = W I2
253.81g/mol
2eq/mol(1000)
3. A sample of stibnite containing 70.05% is given out for analysis. A student titrate it
with a soln of I 2 which 1.000 mL is equivalent to 0.004946 g of AS2O3.Due to an
error in standardization, the student’s analysis shows the sample to contain
70.32% Sb. Calc the true normality of the I 2 and the percentage error in the
analysis.
me I2 = me As2O3
1mL (N I 2) = 0.004946 g
197.84 g/mol
4eq/mol(1000)
N I2 = 0.10 N
% error = 70.32 - 70.05 x 100

70.05
= 0.385 %
4. Wt. of copper ore taken for analysis = 1.200 g; vol of Na 2S2O3 used= 40.00 mL; 1mL
Na2S2O3 ≎ 0.004715 g KBrO3. Calc. the copper content of the ore in terms of percentage
Cu2O.
me Cu++ → me Cu2O → me Na2S2O3
me Na2S2O3 → me KBrO3
1mL( N Na2S2O3) = 0.004175 g

167.01 g/mol
6 eq/mol(1000)

N Na2S2O3 = 0.15 N
% Cu2O = (mL Na2S2O3 x V Na2S2O3 x me wt Cu2O x 100

W sample
% Cu2O = (40 mL)(0.15N) 143.08g/mol
2eq/mol(1000) x 100
1.2 g
% Cu2O = 35.77 %
5. What is the percentage of Sb in a 0.2500-g sample of stibnite if 20.83 mL of I 2 are used

in the final titration and each milliliter of the I 2 is equivalent to 0.004495 g of As ?
me I 2 = me As
1mL( N I 2) = 0.004495 g
75 g/mol
2eq/mol(1000)
N I2 = 0.1198 N
% Sb = V I 2 x N I 2 x me wt Sb x 100
W spl
% Sb = ( 20.83 mL)(0.1198 N) 122 g/mol

2eq/mol(1000) x 100
0.25 g
= 60.87 %
6. What volume of thiosulfate soln ( 1.00 mL ≎ 0.004873 g of potassium biiodate) will be

required to titrate the I 2 liberated by the Cl2 evolved when a 0.450- g sample of red
lead containing 95. 0% Pb3O4 is boiled with HCl ?
me thiosulfate =me KIO3. HIO3

IO3 ( +5) → I- (-1) f= 5-(-1)= 6x2=12
1mL (N thio) = 0.004873 g

75 g/mol
12eq/mol(1000)
N thio = 0.15 N
0.45 g red lead + HCl → Cl2 + x’s KI → I2
(contg 95% Pb3O4) O.A + Na2S2O3

NaI + Na2S4O6
me Pb3O4 = me Cl2 = me I2 = me Na2S2O3

0.45g (0.95)
685.57 g/mol = 0.15 N ( V thio)
2eq/mol(1000)
Pb3O4 : PbO2 (+4) + 2e- =→ Pb ( +2) p.277
V thio = 8.31 mL
REF SEA-BSCHE-CHE526-2020
MODULE 7: GRAVIMETRIC ANALYSIS

GRAVIMETRIC ANALYSIS


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MODULE IN

Department of Chemical Engineering

SCHOOL OF ENGINEERING AND ARCHITECTURE

MODULE 6: VOLUMETRIC METHODS OF ANALYSIS:UNIT 1: ACIDIMETRY AND

UNIT 1: INTRODUCTION: TITRATION CONCEPTS

DIVISIONS OF ANALYTICAL CHEMISTRY:

a. Qualitative Analysis - nature of the constituents of a given material

b. Quantitative Analysis - proportion in which these constituents are present

-measures the mass of a substance chemically related to the

DIVISIONS OF QUANTITATIVE ANALYSIS:

2. Gravimetric Analysis - based entirely upon weight, the original substance

Prepared by: LRRAMOS

4. Other physicochemical Methods - quantities of constituents from

5. Gas Volumetric Methods - determination of a mixture of gases

1. Neutralization methods – acidimetry (acid determination) and alkalimetry (alkali

Titration – determination of the concentration (unknown) of a solution by the

titrant – solution of known concentration (reagent solution)

analyte – substance under study (substance being titrated)

Standard solution – solution whose concentration is accurately known

Prepared by: LRRAMOS

b. standard alkali solutions:

Standardization – process of determining the exact concentration of a titrant

Primary standard – a substance of highest purity used for standardization

example: potassium hydrogen phthalate (KHP) or KHC8H4O4 ; sodium

Indicator – a substance (colored dye) that is sensitive hydrogen ion concentration,

example: phenolphthalein, methyl orange, congo red, bromocresol

• Equivalence point – the point in titration in which the chemical reaction is

Prepared by: LRRAMOS

• equivalents, E = weight of solute .

equivalent weight of solute

also: equivalents,E = N X V in liters

Note: N = eq/ L = meq/mL

Equivalent weights in Neutralization Methods

fundamental reaction of acidimetry and alkalimetry is:

- the neutralization of an acid by a base or the neutralization of a base by an acid

• equivalent weight of a substance acting as an acid is that weight of it which is

• Equivalent weight of a substance acting as a base is that weight of it which will

equivalent weight of solute = molecular weight

Recall: factor determination:

acid – the number of H+ replaceable

HCl f=1 H2SO4 f=2

HC2H3O2 f=1 H3PO4 f=3

base – the number of OH- replaceable

NaOH f=1 Al(OH)3 f=3

Others: needed in precipitimetry, redox, compleximetry

salt – the total positive charge

Prepared by: LRRAMOS

redox – change in oxidation state

Mn+2 Mn+7 f=5

DETERMINATION OF NORMALITY OF SOLUTION

or N = W (g) solute x f solute

equivalents of acid = equivalents of base

or milliequivalents of acid = milliequivalents of base

me solid = w (g) solid

(1) 1 LIQUID / 1 LIQUID

(2) 1 LIQUID / 1 SOLID

Prepared by: LRRAMOS

Prepared by: LRRAMOS

CASE I: solution B (acid)

Solution A (acid) Resulting solution (R.S )

meq A (acid) + meq B (acid) + meq C (acid) = meq R.S. (acid)

A, B, C & R.S. could be bases too..