7. Volumetric Analysis
Solution of accurately known strength is called
standard solution.
Substance for preparing primary standard
solution is called primary standard substance.
Substance whose standard solution can’t be
prepared by direct weighing is called……….
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14. Volumetric Analysis
Process of determine strength of unknown
solution (titrate) with the help of standard
solution (titrant) is called titration.
The difference between end point and
equivalence point is called titration error.
The point at which the indicator changes color
is called the endpoint. So the addition of an
indicator to the analyte solution helps us to
visually spot the equivalence point in an acid-
base titration
14Tej narayan chapagain 8/25/2020
15. The equivalence point is the point in
a titration where the amount
of titrant added is enough to
completely neutralize the analyte solution.
The moles of titrant (standard solution)
equal the moles of the solution with
unknown concentration.
This is also known as the stoichiometric
point because it is where the moles of acid
are equal to the amount needed to
neutralize the equivalent moles of base
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16. Normality factor
Normality factor is defined as the ratio
of observed wt. of solute to the
theoretical wt. of the solute required to
prepare a solution of desired normality.
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17. Titration curve
Plot of pH of solution against volume of
base added. The middle steep rise indicates
the pH at which acid and base neutralize
each other.
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19. The process of determining strength of acid
solution volumetrically by titrating with
standard alkali in presence of indicator is
called acidimetry.
The process of determining strength of
alkali against standard acid solution is
called alkalimetry.
Chemical substances (weak bases) which
indicates end point of reaction by changing
their colors is called an indicators.
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20. Contd…
Generally, in acid-base titration, organic
complex chemical substances are taken as
indicator.
Indicator have different colour in ionized and
unionized form.
Different indicators have different pH-range
at which there is sharp change in colour.
Litmus paper, methyl orange,
phenolphthalenin etc. are the common
indicators.
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21. Types of indicators
Internal indicators- Internal indicator is an indicator
which is dissolved in the solution where main reaction is
taking place.Eg-i. acid – base indicator
(phenolphthalein, methyl orange, litmus etc.),
ii. self indicator(when one of the reactant in titration can it
self act as indicator-eg-KMnO4 in titration with oxalic
acid in acidic medium),
iii. absorption indicator etc.
External indicator- those indicators which are not added
to solution , but used externally are termed as external
indicators. Eg- potassium- ferricyanide in titration of
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22. Potassium dicromate and ferrous
salt.
Characteristics of good indicator (IMP)
The color should change over a short pH
range.
The color should change at the end point of the
reaction.
The suitability of indicators depend on the
nature of acids and bases involved in titration.
The color change should be sharp and stable.
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23. Common indicators and their pH ranges
Indicator in acidic med. In basic med. pH-range
M.Orange red yellow 3.1-4.4
M.Red red yellow 4.2-6.3
P.Phthalein colorless pink 8.2-10
L. Paper red blue 5.5-8.0
Where, M= methyl
P= phelnol
L= litmus
med = medium pH-range=working pH
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24. Selection of indicator in acid-base titration
If alkali is taken in burette and acid in conical
flask , then the pH of the resulting solution is
gradually increases while adding alkali on
acid.
If pH of the resulting solution is plotted
against the volume of alkali added, then the
plots obtained are called pH-curves or titration
curves.
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25. Contd…
The nature of the pH-curves or sharpness in
the pH curves help to select the suitable
indicator.
The nature of pH curves depends on the acids
and bases taken during titration.
The pH curves are shown in the fig.
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27. When strong acid is titrated against strong
base, then the nature of the pH-curve is shown
above. there is sudden change in pH from 3-
11.
Therefore, the indicators like phenolphthalein
having pH range 8.2-10, methyl orange having
pH range 3.1-4.4 and litmus paper with pH
range 5-8 can be choosen as suitable indicator.
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29. When strong acid is titrated against weak base,
then the curve formed is shown above. There
is sudden increase in pH from 3-8.
Therefore , methyl orange having pH range
3.1-4.4 is only suitable indicator.
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31. When weak acid is titrated against the strong
base then the curve obtained is shown above.
There is sudden increase in pH from 6-11.
therefore phenolphthalein having pH range
8.2-10 is only suitable indicator.
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33. When weak acid is titrated against weak base,
then the curve obtained is shown above.
There is no sharpness in the curve and none of
the indicator can be choosen.
Therefore, the titration between weak acid and
weak base is not carried out.
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34. Q. Why is phenolphthalein suitable indicator
for weak acid Vs strong base titration?
Answer,
– experimentally, the pH curve of weak acid and
strong base is found to range from 6-11. so the
phenolphthalein having pH range 8.2-10 lie in
this interval can detect the end point of
reaction by sharp change in color. that’s why ,
phenolphthalein is suitable indicator for weak
acid and strong base titration.
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35. Q. None indicators are suitable indicators for
weak acid and weak base titration, why?
Answer,
- Experimentally, the pH curve for weak acid
and weak base titration is not found to be
sharp. So, None indicators are suitable
indicators for weak acid and weak base
titration.
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36. Q. Why are both methyl orange and
phenolphthalein suitable indicator for
strong Vs strong base titration?
Answer
- Experimentally, the pH curve of strong acid
and strong base is found to range from 3-11.
so the methyl orange having pH range 3.1-4.4
and phenolphthalein having pH range 8.2-10
lie in this interval can detect the end point of
reaction by sharp change in color . That’s why,
both methyl orange and phenolphthalein are
suitable for strong acid and weak base titration.
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37. Q. Calculate the weight of oxalic acid required to
prepare 250ml of decinormal(N/10) solution.
Solution-
volume of soln to be prepared(V)=250ml
Normality of soln(N) = 1/10
Eq.wt of oxalic acid(E) = 63
Wt. of oxalic acid required(W) =?
since, W=VEN/1000
1.575g
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38. Problem
Q.1. 20ml of sulphuricacid needs 0.106g of
Na2CO3. Calculate the normality of acid.
Soln- 0.1N
Q.2. 0.04 g of pure caustic soda was found to be
required to neutralize 10cc of dilute H2SO4.
calculate the concentration of acid solution in
terms of
a) normality b) g/l c) molarity
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39. Q.4. calculate the volume of conc. Sulphuric
acid required to prepare N/10 solution of it
in 250 ml of water.
Q.5. x g of calcium carbonate required 20ml
of 2N hydrochloric acid. Calculate the value
of x.
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41. Derivation of normality equation
• We know, normality=no. Of gram equivalent÷
litre of solution
• No. Of g equivalent = litre of solution× normality
at the equivalent point of titration
• No. Of g eq. Of acid=No. Of g eq. Of base
• Or, litre of acid solution×normality of acid=litre of
base solution×normality of base
• Or, 1000 ml of acid solution× normality=1000 ml
of base×normality of base
• Or, ml of acid solution×normality of acid=ml of
base solution×normality of base
• Or, V1N1=V2N2 This is normality equation.
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43. Expression of concentration
Concentration measures quantity of solute
present in given volume of solution.
a) Gram per litre(g/l)
gram per litre of a solution is defined as the
weight of solute in gram present present in
one litre of a solution.
gram /litre= Wt. of solute in gm/volume of
solution in litre
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45. Molarity(M)
Molarity of a solution is defined as the number
of gram moles of solute present in one litre of
a solution . It is denoted by M. it decreses with
rise of temperature , as it depends upon
volume of solution.
Molarity =NO. of gram moles of solute /
volume of solution in litre
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52. Molar solution
If one litre of soln contains one gram moles of a
solute , then it is said to be molar solution.
Eg. 1M soln of H2SO4 means 98g of it present
in one litre soln.
Deci-molar soln(M/10) -The soln in which one
tenth of gram molecular weight of solute
present in one litre of a solution. Eg.M/10 of
NaoH means 4gm of it present in 1L of soln.
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53. Semi-molar solution(M/2) – the soln in which
half gram moles of solute present in one litre
of soln.
Eg. M/2 NaOH soln means 20gram of it present
in 1L of soln.
Note;
No. of moles = wt. in gm
molecular wt.
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55. when 1/2 gram equivalent of the solute is
dissolved in 1 litre of the solution it is called
as seminormal solution. it is denoted by N/2.
Deci normal solution : When one-tenth gram
equivalent mass of a substance is present in
one litre of its solution then it is
called decinormal solution .
Note ;
No. of gm eq = wt. in gm
eq.wt
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56. N/100 ( centi normal ) = When 1/100
gm.equivalents of solute are present in one
liter of solution,then solution is centinormal.
N/1000 ( milli normal ) = When 1/10oo
gm.equivalents of solute are present in one
liter of solution,then solution is milli
normal.
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57. Normality Formula
Normality = Number of gram equivalents × [volume of solution in litres]-1
Number of gram equivalents = weight of solute × [Equivalent weight of solute]-1
N = Weight of Solute (gram) × [Equivalent weight × Volume (L)]
N = Molarity × Molar mass × [Equivalent mass]-1
N = Molarity × Basicity = Molarity × Acidity.
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58. Calculation of Normality in Titration
Titration is the process of gradual
addition of a solution of a known
concentration and volume with another
solution of unknown concentration until the
reaction approaches its neutralization. To
find the normality of the acid base titration
N1 V1 = N2 V2
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59. Where,
N1 = Normality of the Acidic solution
V1 = Volume of the Acidic solution
N2 = Normality of the basic solution
V3 = Volume of the basic solution
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60. Normality Equations
The equation of normality that helps to estimate
the volume of a solution required to prepare a
solution of different normality is given by,
Initial Normality (N1) × Initial Volume (V1) =
Normality of the Final Solution (N2) × Final
Volume (V2)
Suppose four different solutions with the same
solute of normality and volume are mixed;
therefore, the resultant normality is given by;
NR = [NaVa + NbVb + NcVc + NdVd] ×
[Va+Vb+Vc+Vd]-1
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61. If four solutions having different
solute of molarity, volume and
H+ ions (na, nb, nc, nd) are mixed
then the resultant normality is
given by;
NR = [naMaVa + nbMbVb +
ncMcVc + ndMdVd] ×
[Va+Vb+Vc+Vd]-1.
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62. % (w/v)
The number of grams of solute present in
100ml of solution is called % (w/v).
% (w/v) = wt. of solute in gm X 100
vol. of soln in ml
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63. % (w/w)
The number of grams of solute in 100 gm of
solution is called % (w/w)
% (w/w) = wt. of solute in gm x 100
wt. of solution in gm
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64. Molality
Number of moles of solute present in
1000gm of solvent is called molality.
Molality = no. of moles of solute X 1000
wt. of solvent in gm
Note;
No. of moles = wt. in gm
molecular wt.
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65. Formality
No of gm formula wt. of solute present in one
litre solution is called formality.
Formality = no. of gm formula wt
vol. of soln in litre
= no. of gm formula wt X 100
vol. of soln in ml
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66. Gram per litre and %(w/v)
1. gm/litre = %(w/v) X10
2. Gm/litre = normality X eq.wt
= molarity X molecular wt
= %(w/v) X10 X specific gravity
A.1. A solution of caustic soda contains 5g of
NaOH per litre. Find the normality of
solution.
5/40=0.125
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67. • Q.1 . 25 ml of soln contain 0.106g of Na2CO3.
calculate normality and molarity.
• Q.2. Commercial sulphuric acid is 98% by wt
and its specific gravity is 1.84. calaulate the
molarity and normality of commercial
sulphuric acid.
• Q.3. A soln of NaOH is found to contain 20g of
NaOH in 250ml. Calculate the concentration of
solution in gm/l and percentage.
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68. Differences Between Normality and Molarity
Normality
Also known as equivalent concentration.it is
defined as the number of gram equivalent per
litre of solution..It is used in measuring the
gram equivalent in relation to the total volume
of the solution. The units of normality are N or
eq L-1
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69. Molarity
Known as molar concentration.It is defined
as the number of moles per litre of solution.It
is used in measuring the ratio between the
number of moles in the total volume of the
solution.The unit of molarity is M or Moles L-1
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71. Normality Problems and Examples
Question 1. In the following reaction calculate
and find the normality when it is 1.0 M H3PO4
H3AsO4 + 2NaOH → Na2HAsO4 + 2H2O
Question 2. Calculate the normality of 0.321 g
sodium carbonate when it is mixed in a 250 mL
solution.
Question 3. What is the normality of the
following?
0.1381 M NaOH
0.0521 M H3PO4
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72. Question 4. What will the concentration of
citric acid be if 25.00 ml of the citric acid
solution is titrated with 28.12 mL of 0.1718
N KOH?
Question 5. Find the normality of the base if
31.87 mL of the base is used in the
standardization of 0.4258 g of KHP (eq. wt =
204.23)?
Question 6. Calculate the normality of acid if
21.18 mL is used to titrate 0.1369 g
Na2CO3?
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73. 1
Solution:
If we look at the given reaction we can identify
that only two of the H+ ions of H3AsO4 react
with NaOH to form the product. Therefore, the
two ions are 2 equivalents. In order to find the
normality, we will apply the given formula.
N = Molarity (M) × number of equivalents
N = 1.0 × 2 (replacing the values)
Therefore, normality of the solution = 2.0.
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74. 2
Solution:
First, you have to know or write down the
formula for sodium carbonate. Once you do this
you can identify that there are two sodium ions
for each carbonate ion. Now solving the problem
will be easy.
N of 0.321 g sodium carbonate
N = Na2CO3 × (1 mol/105.99 g) × (2 eq/1 mol)
N = 0.1886 eq/0.2500 L
N = 0.0755 N
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75. 3/4
Solution:
3/a. N = 0.1381 mol/L × (1 eq/1mol) = 0.1381 eq/L = 0.1381
N
3/b. N = 0.0521 mol/L × (3 eq/1mol) = 0.156 eq/L = 0.156 N
4/Solution:
Na × Va = Nb × Vb
Na × (25.00 mL) = (0.1718N) (28.12 mL)
Therefore, the concentration of citric acid = 0.1932 N.
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76. 5
Solution:
0.4258 g KHP × (1 eq/204.23g) × (1 eq
base/1eq acid):
= 2.085 × 10-3 eq base/0.03187 L = 0.6542 N
Normality of the base is = 0.6542 N.
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77. 6
Solution:
0.1369 g Na2CO3 × (1 mol/105.99 g) × (2 eq/1
mol) × (1 eq acid/1 eq base):
= 2.583 × 10-3 eq acid/0.02118 L = 0.1212 N
Normality of the acid = 0.1212 N.
⇒ Try this:
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79. 1. What volume of 6M HCl and 2M HCl
should be mixed to get one litre of 3M
HCl?
• 2. How much volume of 10M HCl should be
diluted with water to prepare 2.00L of 5M
HCl.
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80. Solution(q.1)
Suppose the volume of 6M HCl required to obtain 1L
of 3M HCl = XL
Volume of 2M HCl required = (1-x)L
Applying the molarity equation
M1V1 + + M2V2 = = M3V3
6MHCl+ 2MHCl= 3MHCl
6x+2(1-x) = 3x1
6x+2-2x = 3
4x = 1
x = 0.25L
hence, volume of 6M HCl required = 0.25L
Volume of 2M HCl required = 0.75L
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82. Objective
• Question 1: Which of the following types of titration is not
a simple titration?
• a. Acid-base titrations
• b. Back titration
• c. Precipitation titrations
• d. Complexometric titrations
• Question 2: According to the law of equivalents,
• a.N2V1 = N1V2,
• b.N1V2 = N2V1,
• c.N1V1 = N
• d. V = N2V2,
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83. Objective
• Question 3: Which of the following conditions is nor required for the back
titration to work ?
• a. Compounds ‘A’, ‘B’ and ‘C’ should be such that ‘A’ and ‘B’ react with
each other.
• b. ‘A’ and pure ‘C’ also react with each other but the impurity present in ‘C’
does not react with ‘A’.
• c. Product of ‘A’ and ‘C’ should not react with ‘B’.
• d. Product of ‘A’ and ‘B’ should be ‘C’.
• Question 4: The titration in which an oxidizing agent is made to react with
excess of solid KI and the oxidizing agent oxidizes I– to I2 is known as
• N2(g) + 3H2(g) → 2NH3(g) ?
• a. Iodometry
• b. Iodimetry
• c. Double titration
• d. Back titration
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