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QUANTITATIVE ANALYSIS

• Quantitative analysis is the determination of


the amount or concentration of a substance in
a sample.
• We can examine the Quantitative aspects of
reactions in aqueous solution or solution
stoichiometry using two techniques
• 1. Gravimetric analysis
• 2. Titrations
1. Gravimetric analysis
It is an analytical technique based on the
measurement of mass. Generally this
technique involves formation, isolation and
mass determination of a precipitate. This
procedure is applied to ionic compounds.

The sample containing the component whose


concentration is to be determined is first
dissolved in water (most ionic compounds
dissolve in water).
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Then it is allowed to react with another substance to
form its precipitate of known composition.
Eg AgNO3 (aq) + NaCl (aq) → AgCl (s) + NaNO3 (aq)
Here Cl- is the component whose concentration is to be
determined. NaCl (the original sample containing Cl-) is dissolved
in water and then reacted with AgNO3 to form AgCl precipitate.

The precipitate is then filtered off, dried and weighed.

Knowing the mass and chemical formula of the


precipitate(AgCl) formed, we can calculate the mass of a
particular chemical component (anion or cation) of the original
sample.

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From the mass of the component (Cl-) and the mass of
the original sample (NaCl) , we can determine the
percent composition by mass of the component in the
original sample.

Gravimetric analysis is a highly accurate technique


because mass of a sample can be measured accurately.
This procedure is applicable only to reactions that form
insoluble precipitate of the desired component.

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Gravimetric Analysis
1. Dissolve unknown substance in water
2. React unknown with known substance to form a precipitate
3. Filter and dry precipitate
4. Weigh precipitate
5. Use chemical formula and mass of precipitate to determine
amount of unknown ion

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Problems

1. A 0.5662g sample of an ionic compound containing


chloride ions and an unknown metal is dissolved in
water and then treated with an excess of AgNO3. if
1.0882g of AgCl precipitate forms, what is the percent
by mass of Cl in the original compound?

SOLUTION: SEE NOTE BOOK

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Problems

2. Calculate the mass of AgBr formed if a solution


containing 6.00g KBr is treated with an excess of
AgNO3.
SOLUTION
The balanced equation is
KBr (aq) + AgNO3 (aq) → AgBr (s) + KNO3 (aq)

Strategy: Since AgNO3 is in excess, KBr is the Limiting


reagent.

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Problems

Mass of KBr→moles KBr→moles of AgBr→mass of AgBr


6.00 g KBr* 1 mol KBr * 1 mol AgBr * 187.77g AgBr
119.002g KBr 1 mol KBr 1 mol AgBr
= 9.47 g AgBr

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2. TITRATIONS
We are interested in two types of
titrations
1. ACID BASE TITRATIONS
2. REDOX TITRATIONS

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In Acid base titrations, quantitative studies of acid base
neutralisation reactions are carried out.

In Titration, a solution of accurately known


concentration, called a Standard solution, is added
gradually to another solution of unknown
concentration, until the chemical reaction between the
two solutions is complete.

Knowing the volumes of the standard and unknown


solutions used in titration and concentration of the
standard, we can find the concentration of the
unknown solution.

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Acid-Base Titration

Titration Base
• is a laboratory (NaOH)
procedure used to
determine the molarity
of an acid.

• uses a base such as


NaOH to neutralize a
measured volume of
Acid
an acid.
solution
Copyright © 2009 by Pearson Education, Inc.

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Indicator

An indicator

• is added to the acid in the


flask( here colourless)

• causes the solution to


change color when the acid
is neutralized.

• Indicators are substances


that have distinctly different
colours in acidic and basic
media.
Copyright © 2009 by Pearson Education, Inc.

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End Point of Titration

At the equivalence point (end


point), the point at which the acid
has completely reacted or been
neutralised by the base
• the indicator gives the solution a
permanent different color (here
pink).
• the volume of the base used to
reach the end point is measured.
• the molarity of the acid is
calculated using the neutralization
Copyright © 2009 by Pearson Education, Inc.
equation for the reaction.
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Calculating Molarity

What is the molarity of an HCl solution if 18.5 mL of


0.225 M NaOH are required to neutralize 10.0 mL of HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

STEP 1: Given: 18.5 mL of 0.225 M NaOH; 10.0 mL of HCl


Need: Molarity of HCl

STEP 2: 18.5 mL L moles NaOH moles HCl M HCl


L HCl
STEP 3: 1 L = 1000 mL 0.225 mole NaOH/1 L NaOH
1 mole HCl/1 mole NaOH

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Calculating Molarity (continued)

STEP 4: Calculate the molarity of HCl.


18.5 mL NaOH x 1 L NaOH x 0.225 mole NaOH
1000 mL NaOH 1 L NaOH

x 1 mole HCl = 0.00416 mole HCl


1 mole NaOH

MHCl = 0.00416 mole HCl = 0.416 M HCl


0.0100 L HCl

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Learning Check

Calculate the mL of 2.00 M H2SO4 required to


neutralize 50.0 mL of 1.00 M KOH.

H2SO4(aq) + 2KOH(aq) K2SO4(aq) + 2H2O(l)

1) 12.5 mL
2) 50.0 mL
3) 200. mL

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Solution

1) 12.5 mL
0.0500 L KOH x 1.00 mole KOH x 1 mole H2SO4 x
1 L KOH 2 mole KOH

1 L H2SO4 x 1000 mL = 12.5 mL


2.00 mole H2SO4 1 L H2SO4

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Learning Check

A 25.0 mL sample of phosphoric acid is neutralized by 42.6


mL of 1.45 M NaOH. What is the molarity of the phosphoric
acid solution?

3NaOH(aq) + H3PO4 (aq) Na3PO4(aq) + 3H2O(l)

1) 0.620 M
2) 0.824 M
3) 0.185 M

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Solution

2) 0.824 M
0.0426 L x 1.45 mole NaOH x 1 mole H3PO4
1 L 3 mole NaOH
= 0.0206 mole H3PO4

0.0206 mole H3PO4 = 0.824 mole/L = 0.824 M


0.0250 L

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Learning Check

How many mL of a 0.610 M NaOH solution are


needed to neutralize 20.0 mL 0f a 0.245M H2SO4
solution?

STRATEGY Write balanced equation between NaOH


and H2SO4

2NaOH (aq) + H2SO4 (aq) → Na2 SO4 (aq) + 2H2O (l)

2 mole NaOH equivalent to 1 mole H2SO4


Molarity of H2SO4 → mol of H2SO4 → mol of NaOH →
volume of NaOH in L → volume of NaOH in mL

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Learning Check

20*10 -3L H2SO4 X0.245 mol H2SO4 X2 mol NaOH X1L NaOHsolnX1000mL
1 L H2SO4 1 mol H2SO4 0.610 mol NaOH 1L

= 20* 10 -3 * 0.245 * 2 * 1000/ 0.610

= 16.1 mL NaOH

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REDOX TITRATIONS
1. Just as an acid can be titrated against a base, we can
titrate an oxidising agent against a reducing agent
using a similar procedure.
2. The equivalence point is reached when the reducing
agent is completely oxidised by the oxidising agent.
3. Like acid –base titrations, redox titrations normally
require an indicator that clearly changes colour at the
end point.
4. They require the same type of calculations (based on
mole method) as acid base neutralisation reactions.

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Two common oxidising agents are
KMnO4 (potassium permanganate) and K2Cr2O7 (potassium
dichromate). The colour of the permanganate and
dichromate anions are distinctly different from those of
their reduced forms.
MnO4 - (purple) → Mn2+ ( light pink)

Cr2O7 2- (orange yellow) → Cr3+ (green)

These can themselves act as an internal indicator in redox


titration because of their different colours in oxidised and
reduced forms. (problems)

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Learning Check

A 16.42 mL of 0.1327 M KMnO4 solution is needed to


oxidize 25.00 mL of a FeSO4 solution in an acidic
medium . What is the concentration of the FeSO4
solution in molarity ? The net ionic equation is

5Fe 2+ + MnO4- + 8H+ → Mn2+ + 5 Fe3+ + 4H2O

SOLUTION
From net ionic equation, 1 mol MnO4- chemically
equivalent 5 mol Fe 2+

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Learning Check

Strategy: Molarity of MnO4- → moles of MnO4- →


mol of Fe 2+ → molarity of Fe 2+

= 16.42* 10-3 LKMnO4 X 0.1327 mol KMnO4 X5 molFeSO4X 1


1 L KMnO4 soln 1mol KMnO4 25*10-3L FeSO4

= 16.42 * 10-3 * 0.1327 * 5 * 1000/ 25


= 0.4358 M

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Determining concentration from intensity of
colour (of a coloured solution)

 Consider a CuSO4 solution (blue coloured)of


concentration say 10 M.
 The intensity of the blue colour of the Cu2+ decreases
as we dilute the solution

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 The colour of Cu2+ arises from the absorption of some regions of
visible light ( composed of colours of 7 wavelengths- VIBGYOR)
and the transmittance of the complimentary colour (here blue)

 According to Beer’s law, the Absorbance A is a measure of the


intensity of colour and hence a measure of the solution
concentration.
Beer’s law relates Absorbance (A) to three quantities
 Concentration (c)
 Path length that the light travels through the solution(b) and
 a constant called the molar absorptivity ɛ (characteristic of the
dissolved solute)
A= ɛbc

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 Absorbance is measured using a spectrophotometer
or a colorimeter instrument.
 The sample solution whose A has to be measured is
placed in a sample cell of fixed length ‘b’, typically 1cm

 Since ɛ is a characteristic of the solute and hence a


constant, A is directly proportional to c( concentration)
 Thus measuring the A of different known
concentrations, c, of the sample solution (of the same
solute) and plotting a graph of A (y axis) and
concentration ‘c’ (x axis) yields a straight line whose
slope gives the value of ɛ

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Such a graph is called a
calibration curve
 Once a calibration graph is generated, the
concentration of an unknown solution of the same
solute can be determined by measuring its
absorbance, Aunk and then finding the x
value(concentration c) corresponding to Aunk from the
calibration curve.

 This method of analysis is called spectrophotometry

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