Unit 6 - Introduction To Volumetric Analysis - Subjects
Unit 6 - Introduction To Volumetric Analysis - Subjects
Unit 6 - Introduction To Volumetric Analysis - Subjects
Objectives
Introduction
aA tT products
Solution :
2 NaOH + H2SO4 Na2SO4 + 2 H2O
This method is limited and less sensitive so it can not be used for dilute solutions.
(2) Specific indicators : Each one of these indicators produce a colored product with only
one substance e.g starch forms blue complex with iodine and thiocianate SCN forms red
complex with iron (III) as we will see later . These indicators are limited so you may say that
these the only well known specific indicators .
(3) Equilibrium Indicators : : These indicators are found in two forms of different colors and
depend only on the change in the physical property of the titration solution ( conical flask
soln. ) such as pH ( acid base titration )
HIn H+ + In-
(color A) (color B)
Regardless of the nature of the titration reaction reactants or product . This type of
indicators will be discussed in detail in later lectures
Primary Standard
primary standard is a substance that is 100 % pure or its purity is well known .
For example, if the weight required for the preparation of a substance solution
is 9.5 g and if the substance powder is 100% pure we weigh 9.5 g and dissolve
it in the desired volume to get a standard solution . But if it is let us say 95%
pure in this case to get 9.5 g of this substance we have to weigh 10 g of the
substance powder . But If it is not pure and its purity is accurately unknown in
this case we weigh 9.5 g and dissolve it in the desired volume and then
standardize this solution with another standard reagent solution to fined its real
concentration .This is what is called standardization . Note that if the substance
is pure or its purity is well known there will be no need for standardization .
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Standard Solution
As mentioned earlier the solution, which is usually placed in the burette is called
standard or reagent or titrant solution . Its concentration must be exactly known
because any error in the preparation of this solution will be reflected on the result
of the analysis and therefore needs to be a 100 % true . Not any substance can be
used as a titrant only the substance that has the following requirements :
(1) It should preferably be primary i.e it is pure or its purity is well known in order
to avoid the process of standardization .
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Standard Solution
(2) Its solution should preferably be constant i.e not affected by the components
of the air or heat so you do not need to standardize it or prepare it daily .
(3) It should be available at a reasonable price and its solution is easy to prepare
.
(4) It should meet the titration reaction requirements which we will discuss later
.
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Standard Solution
(5) Its molecular weight preferably be high in order to reduce the weighing
error . For example to prepare one liter of 1.0 M of NaOH ( mw = 40 g )
we will weigh 40 g of NaOH , while if we want to prepare one liter of 1.0
M of Ba(OH)2 [ mw = 171 g ] we will weigh 171 g . Since the balance
error is constant , let us say 0.001 g , its effect on NaOH will be more
compared to Ba(OH)2 .
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Titration Reaction
Not any chemical reaction can be used in the volumetric analysis. There
are some conditions to be met in order for a chemical reaction to be used
as a basis for a titration :
Titration Reaction
Titration Reaction
2. Oxidation-Reduction Titrations :
AOx + BRed ARed + BOX
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Titration Reaction
3. Precipitation Titrations :
aA + b B dD
After adding the indicator and titrating to the endpoint where the indicator
changes its color we record the titrant volume from burette mlB Let us assume
that equivalent point endpoint .
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From the above equations , we can calculate the molarity of the analyte solution MA
if it is required :
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But if we weigh let us say z mg of a sample containing the analyte A and transferred this
weight to the conical flask to titrate it after dissolution then the required could be the
percentage of A in the sample :
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In almost all cases , a burette is used to meter out the titrant B volume
( mlB ). When a titrant reacts directly with an analyte A , the procedure is
termed a direct titration. The alternative technique is called a back
titration. Here, an intermediate reactant E is added in excess of that
required to exhaust the analyte A , then the exact degree of excess is
determined by subsequent titration of the unreacted intermediate E with
the titrant B . Another technique is called replacement as we will see
shortly .
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1- Direct Titration :
In this method as mentioned earlier the titrant
reacts directly with the analyte usually in the
conical flask in the presence of an indicator .
Solution :
Every 100 mg of Na2C2O4 contain only 95 mg pure Na2C2O4
Then 300 mg = = = = = = = = = x mg = = = = =
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Solution :
2- Back Titration :
Back titration is used when the analyte either does
not react with the standard solution B or reacts too VIDEO VIDEO
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In this event, a previously known excess of another standard solution E is added to the
analyte, and the residue of E after the reaction with the analyte A is complete is titrated with
the standard solution B : aA + eE ....
at eq.p 0 excess
e E ( excss ) + bB
at eq.p 0 0
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After separating the Ag2CrO4 precipitate , the excess Ag+ in the filtrate was titrated with
0.12 M of SCN solution according to the following equation :
Ag+ + SCN- AgSCN
At eq.p 0 0
If the volume of SCN- solution was 14.5 mL , calculate the %w/w percentage of Cr2O3
( mw = 152 ) in the sample ?
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Back titration
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Replacement Titration :
Titration by substitution is used when direct titration of the analyte is difficult, as is the
case when no suitable titrant or essential indicator is available. In this event, a reaction with
an undetermined excess of a suitable reagent E is used to convert the analyte A into
another compound D :
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aA + eE dD
(C) 0 excess produced
The produced D is titrated by the standard solution B :
dD + bB R
At eq. p. 0 0
Using the second reaction we can calculate the produced D and from the first
reaction we calculate the amount of A as is shown by the following examples .
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Example : 750 mg of a sample containing iron ( aw = 55.85 ) was transferred into a titration
conical flask and all iron was converted to Fe3+, then unknown excess of KI was added and
the following reaction was occurred :
2 I- + 2 Fe3+ I2 + 2 Fe2+
The iodine I2 formed was titrated with 0.075 M of Na2S2O3 solution using starch as indicator
according to the following reaction equation :
I2 + 2 S2O32- 2 I- + S4O62-
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Solution :
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2Cu2+ + 4 I- 2 CuI + I2
The liberated I2 is titrated with the unknown Na2S2O3 solution using starch as indicator
according to the equation :
I2 + 2 S2O32- 2 I- + S4O62-
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If the volume of Na2S2O3 solution at the equivalent point is 44.9 mL , calculate the
molarity of NaS2O3 solution ?
Solution :
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aA + b B eE
solution ( containing every thing except the sample ) needed 0.08 mL for the color of KMnO4
to appear in the titration flask solution , calculate the percentage of the indicator error ?
Solution : Since Ti3+ was coverted to Ti4+ then the number of active units h = 1 :
At equivalent point :
= mLMnO4- X NMnO4-
= 27.45 X 0.02631
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To correct for the indicator error we subtract the blank volume Vblank from the volume at the
end point Vend p. in order to calculate the volume at the equivalent point Veq.p :
Titration Curve
Titration curve is very important where it gives an idea of how successful the
titration is . It is also useful in the selection of the appropriate indicator for
titration . However , it is rarely used to find the volume of reagent solution at
the equivalent point because it is easier to use an indicator and read the volume
from the burette as we shall see . The titration curve can be obtained usually by
drawing a relationship between the volume of the standard solution ( titrant )
mlB ( X-axis) and any property of the titration flask solution ( y-axis) such as
pH ( acid base titration ) or voltage E (oxidation reduction titration) or the
concentration of the analyte pA or the titrant pB ( complexometric and
precipitation titrations ) as we will see later.
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Titration Curve
aA + bB eE , K eq = 1x1010
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Titration Curve
Titration Curve
Titration Curve
Also , one can assume that both [A] and [B] are equal to zero , this assumption is
true since Keq is large . However , both can be calculated as follows :
Titration Curve
Note also that ( mL A + mLB ) represent the solution in the conical flask .
Substituting for [B] from the above equation in the Keq equation we can calculate [A] :
Titration Curve
[A] can be considered equal to zero or can be calculated from the Keq equation :
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Titration Curve
Titration Curve
mmoles B = mmoles A X 2 = 10 X 0.1 X 2 = 2
M = mmoles / V (mL )
0.2 = 2 / Veq.p (mL) Veq.p ( mL) = 10
Titration Curve
[B] and [A] are very small and can be assumed to be zero or we
can calculate them from Keq equation thus :
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Titration Curve
Titration Curve
[A] can be assumed to be equal to zero or can be calculated from the Keq thus :
Titration Curve
If we draw the relationship between the volume of titrant mLB ( X-axis) and the
concentration of each of [E] or [B] or [A] ( y- axis ) we will obtain for each case two straight
lines meet at the equivalent point as shown in the following Figure :
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Titration Curve
1- If you continue to derive the curve as in the previous example, you'll notice that the
relative changes in the concentration of B are small in the regions far from the equivalent
point and great in the regions close to the equivalent point .
Where [B] is the difference between the concentration of B before the change and
after the change . Same thing can be repeated for A .
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Titration Curve
Titration Curve
3- This curve is similar in all types of titrations. The changes in the p function at the
regions near the equivalent point depend on the concentrations of the reactants and the
value of the reaction equilibrium constant Keq.The higher the concentrations and the larger
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Titration Curve
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Titration Curve
4- Instead of pB or pA , we can
use any physical properity of the
conical flask solution such as pH
( acid base titration ) or
potential ( redox titration ) .etc
as will be seen later .
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Summary
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Answer 1 :
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Exercise 3 : When 20 mL of 0.1 M of Na2CO3 is titrated with 0.2 M HCl according to the
following titration reaction :
2HCl + Na2CO3 2 NaCl + CO2 + H2O
Calculate the molar concentration of Na2CO3 in the conical flask solution after adding 5 mL
of HCl solution ?
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Answer 3 :
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Exercise 4 : When 20 mL of 0.1 M of Na2CO3 is titrated with 0.2 M HCl according to the
following titration reaction :
2HCl + Na2CO3 2 NaCl + CO2 + H2O
Calculate the molar concentration of HCl in the conical flask solution ( titration solution )
after adding 50 mL of its solution to the conical flask ?
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Answer 4 :
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Answer 5 :
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Answer 6 :
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Exercise 7 : A sample of steel containing sulfur has been taken for analysis . The sulfur of
the sample is converted to H2S which is absorbed in 10 mL of 0.005 M of I2 where the
following reaction is occurred :
H2S + I2 S + 2I- + 2 H+
The excess I2 is titrated with 0.002 M of S2O32- solution according to the following reaction :
I2 + 2S2O32- 2I- + S4O62-
If the volume of S2O32- solution at the equivalent point is equal to 2.5 mL , calculate the mg
weight of sulfur in the sample ?
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Answer 7 :
Exercise 8 : List the major species in the conical flask solution at points A, B, C, and D on
the following titration curve of the titration of ammonia NH3 with HCl ?
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Answer 8 :
A = NH3, it has yet to be acidified.
B = NH3 and NH4 + in the buffering region.
C = NH4 +. At the equivalence point, all the NH3 has been converted to NH4+ .
D = NH4 + and more HCl in solution .
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Exercise 9 : Why is it acceptable to use an indicator whose pK a is not exactly the pH at the
equivalence point ?
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Answer 9 : As we can see in the following titration curve, even if the pK a of the indicator is
several units away from the pH at the equivalence point, there is only a negligible change in
volume of titrant added due to the steep slope of the titration curve near the equivalence
point ?
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Exercise 12 : Write a description of the general steps for the titration procedure to determine
the molarity of a solution of a substance?
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