VOLUMETRIC ANALYSIS (TITRATION)

(LECTURE)

Titrimetric Analysis
Properties of volumetric process

Qualitative process
Equilibrium lay far to the Right
Fast

Materials

Analytical balance
Volumetric glassware
Indicator (phenolphthalein)

Requirements of volumetric process

Stoichiometric reaction
Rapid reaction
No slide reaction
Marked changed properly.

Titration- a process that involves combining a sample with unknown concentration (analyte) and a reagent
solution of known concentration (titrant).
Titrant- a solution of known concentration added to the analyte.

Prepared by dissolving an accurate weighed quantity of a highly pure substance and diluting to an
accurate known using a suitable solvent in volumetric flask.
Standardization- process of determining the exact concentration of solution.
Primary standard- stable, non- hygroscopic substance that exact qualitatively easy to purify and handle.

High purity
Stable
High molar mass- in order to offset any weigh errors.

Titrant: HCL Titrant:

NaOH
Primary standard: Na2CO3
= I can use HCL to standardized

If titrant is ACID If titrant is BASE

Potassium Hydrogen Sodium
Phthalate (KHP)
Benzoic Acid Tries (hydoxymethyl)
amino
Oxalic Acid dehydrate 4- aminorpyride
Sulfamic acid Sodium oxalate

Secondary substance - solution standardized using a primary standard; less accurate due to titration errors.
Equivalent Point point where just enough titrant has been added to react with the analyte.
 Amount of titrant = amount of analyte
Point at which the reaction is complete

End point- point where reaction is observed to be complete.

Experiment value
Experimental estimation of the equivalence point.
The middle of the two extreme colors of the indicator.

Relationship of equivalence Points & Endpoint

Better if the two are the same or near one another.

Endpoint should coincide with the equivalence

Significance of Titration Curve

To choose proper titrants and indicators.

To decide which ph. calculation should be used.
Shape of the titration curve will determine the success or failure of a titration.

TYPES OF TITRATION

Acid- Base Titration

Also known as neutralization.
Real concept: proton transfer.
Acidimetry- acid substance titrated with a basic solution.
Alkalimetry- basic substance titrated with a standard acidic soln

Acid- base indicators

o Most acid- base indicators are organic days, conjugate acid- base forms have different colors.
o Acid medium- unionized form
o Base medium- conjugate base form.

Example: Phenolphthalein
Acidic- colourless
Endpoint: light pink
Basic- pink
Precipitation Titration
also known as precipity
real concept: formation of precipitate
silver nitrate (AgNO3-) Titrant
Completion Titration
complex formation method
transition metals
EDTA (titrant)
Substance titrated with a standard reagent to the formation of complex ion.
Redox Titration
Real concept: electron transfer
Titration curve variables: electrode potential(V) vs. volume titrant(mL)
Titration curves are not always symmetrical
Cr2O72- or Fe (titrant)

Back titration- condition where excess untreated portion is titrated

Analyte reaction may be speeded up in the presence of excess reagent.
SAMPLE PROBLEM
A 0.1000M AgNo3 was used to titrate a Nalco sample (MM=55.44) and 25.00 mL of the titrant was used. What
is the mass (in mg) of NaCl available in the sample?
AgNO 3+ NaCl AgCl+ NaNO3

% of NaCl if the sample weighs 1.000g

mmol 1 mmol NaCL 58.44 mg 1
0.1000 AgNO 3 25.00 mL 100 =14.61
mL 1 mmol AgNO 3 1 mmol 100 g

Mass f Nalco available in the sample

mmol 1 mmol NaCL 58.44 mg
0.1000 AgNO 3 25.00 mL =146.1 mg
mL 1 mmol AgNO 3 1 mmol

TITRIMETRIC ANALYSIS
mganalyte
TITER= mL titrant

Back Titration (sample problem)

From the ff. data. Find the % cream of tartar (KHC4H4O6)
Wt. Of sample= 1.4160 g
NaOH titrant used= 20.87 mL
HCL used for base titration= 1.27mL

1.00mL HCL 1.12 mL NaOH

1.00 mL HCL 0.01930 g CaCO3

Std. of back titrant

1mol CaCO 3 2 mol HCL 1
0.01930 g CaCO 3 =0.3857
100.8 gCaCo 3 1 mol CaCO3 1000

mmol 1mmol HCL 1

0.3857 HCL 1.00 mL =0.3444 M HCL
mL 1mmol HCL 1.12 mL

mmol 1 mol NaOH 1 mol KHC 4 H 4 O 6 188 mg 1
0.3857 HCL 1.27 mL
mL 1 mol HCL 1 mmol NaOH 1 mol KHC H O 1416.0 mg 100=88.93
4 4 6

[
0.3444
mmol
mL
NaOH 20.87 mL ]
A 1.000g aluminium sample required 20.50 mL EDTA for titration. The EDTA titration was first standardized
by titrating it against a 25.00mL 0.1000M CaCl2 standard, consuming 30.00 mL EDTA. What is the
percentage aluminium oxide available in the sample?
 First compute for the molarity of EDTA.
mmol 1 mmol EDTA 1
0.1000 CaCl 2 25.00 mL =0.08333 M EDTA
mL 1 mmolCaCl 2 30.00 mL
101.96 g Al 2 O3 1
2 mmol Al3 + 100=8.708 Al 2 O3
1mmol Al3 1000 mg
Al3 + 1 mmol Al 2 O3
1 mmol
1 mmol EDTA
0.08333 25.00 mL

Effect of Concentration

The more concentrated the solution used, the steeper the slope at the equivalence point.
More reactant are reacting on the analyte.
Where the indicator relay on the ph of the solution at the equivalence point.

Effect of Reaction Completeness

Determine the value of Ki(acid dissociation constants /Kb( base dissociation constant)
Acid strength decrease as Ka value decreases; slope of the curve becomes less steep.
Relay on the acid/base strength.

ACID-BASE TITRATION
Strong acid and Strong base
HCl+ NaOH NaCl+ H 2 O

Kw= 1.0X10-4
1. before equivalence point
Vbase=0
Analyte: strong acid
Titrant: strong base
Ph of the solution =

PH= Cacid
PH= -log+
PH= -log (conc. of acid) (always
express in molarity)

2. at equivalence point
Analyte: strong acid
Titrant: strong base
Ph of the solution= 7(neutral ph)
3. After the Equivalence point
The system now contains an excess of OH.
 Analyte: strong acid
Titrant: strong base
Ph of the solution

total moles of base ( titrant ) mmol acid(analyte )

pOH=
total volume

pH=14 pOH

Sample Problem
A 25.00mL solution of 0.0920M HCl was titrated with 0.00, 15.00, 23.00 and 30.00mL of 0.1000M
NaOH. What is the ph of the solution at the three stages of titration?

Vol. of titrant pH
0.00 1.04
15.00 1.70
23.00 7.00
30.00 12.1

1. Pre equivalence point (dominated by analyte)

A. VT= 0.00mL
= -log acid

= -log (0.0920M)
=1.04
B. VT= 15.00mL

mmol mmol 1 mmolHCl

C acid =
( 0.0920
mL
HCl 25.00 mL ) (0.1000
mL
NaOH 15.00 mL
1mmol NaOH )
15.00 mL +25.00 mL

C acid=0.0200 M

0.0200 M
pH=log

pH=1.70

2. Equivalence Point (ph is always 7)

* find the volume of the titrant at equivalence point
 mmol 1mmol NaOH 1mL
0.0920 HCl 25.00 mL =23.00 mL
L 1mmol HCl 0.1000 M NaOH

3. Post Equivalence Point

VT= 30.00mL
C= titrant: 0.0127M
POH= -logCbase
=1.90
PH= 14 1.90 = 12.1

(0.1000 mmol
L
NaOH 30.00 mL )

mmol 1mmol NaOH

0.0920 HCl 25.00 mL
L 1mmol HCL



pOH =

ANALOGOUS TO THAT OF A STRONG ACID

Analyte: strong base
Titrant: strong acid
a. Vtitrant = 0.00mL

PH= 14 pOH

B. Vtitrant Vequivalence pt.

C
( b V b )(Ca V a RR)

V total
C base=

C. At Equivalence Point
PH= 7.00

D.Vtitrant Vequivalence pt.

C
( a V a )(Cb V b RR)
V total
pH =log Cacid

SAMPLE PROBLEM
A 25.00m mL solution of 0.1000M NaOH was titrated with 0.00mL, 10.00mL, 25.00mL and 35.00mL of
0.1000M HCl. What is the pH of the solution at the three stages of titration?
1. Pre-equivalence
VT= titrant
VT= 0.00mL
POH = - log (0.1000M NaOH) (strong base)
PH= 14 - 1 = 13

VT= titrant
VT= 10.00 mL

1 mmol NaOH
(
( 0.1000 M NaOH 25.00 mL ) 0.1000 M HCl 10.00 mL
1 mmol HCl )
35.00 mL
0.04285714286
log ( 0.04285714286 )=1.37
pH =141.36=12.64

2. Post Equivalence Point

( 0.1000 25.00 mL )(0.1000 M 25.00 mL rr )

60.00mL
pH =1.77