6 - Titration Curves LBBBIAN

Acid-Base Titration:
Titration Curves
with Sir Adolf

An acid-base titration.
Start of titration Point of Slight excess of

Excess of acid neutralization base
Endpoint
REMEMBER: A significant or remarkable change in
some property of the solution happens at the equivalence
point.
• The end point is chosen so that it coincides or occurs as

close as possible to the equivalence point.
Nonspecific, Equilibrium-dependent
Compounds
Graphic Endpoint
Specific Compound Formers
Colored Titrants/Analytes
Titration Curves
• The two most widely used end
points involve (1) changes in color
due to the reagent, the analyte,
or an indicator and (2) a change in
potential of an electrode that
responds to the concentration of
the reagent or the analyte.
• A sigmoidal curve, important

observations are confined to a small
region (typically ± 0.1 to ± 0.5 mL)
surrounding the equivalence point.
• Linear segment curve, measurements
are made on both sides of but well
away from the equivalence point.
Measurements near equivalence are
avoided.
Titration Curve
• Plot of some property of

the titration mixture that
changes as the reaction
progresses
• For acid-base reactions,

the titration reaction is
monitored by measuring
the pH of the mixture as
increasing volumes of
the titrant are added
5
General Shapes of a Titration Curve
Sigmoidal curve or S curve:

consists of 2 lines that are parallel to one another
Titration Curve of 25.00 mL of 0.120 M HCl with 0.100 M NaOH
14.000
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
General Shapes of a Titration Curve
Sigmoidal curve or S curve:

consists of 2 lines that are parallel to one another
14.000
12.000
10.000 pH break or pH transition

pH break range:
8.000
A sudden change in the pH of

pH
6.000
the solution causes the slope of

the line to change
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Stoichiometric Relationship Between
the Analyte and the Titrant
• The number of inflection points (or steep portions) of the
titration curve is an indication of the stoichiometric ratio
between the analyte and the titrant.
14.000
12.000
10.000
Inflection points
8.000
pH
6.000
4.000 Inflection point

2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Stoichiometric mole ratio (SMR) between

the analyte and the titrant is 1:1
Diequivalent Base titrated with a Strong Acid
Inflection points
Four Stages of the Titration Curve
Strong Acid-Strong Base Reaction
14.000
Before
12.000
Equivalence
Point Stage 25.00 mL of 0.120 M HCl
10.000 0 < VT < VEP

After Equivalence
8.000
point stage VT > VEP
pH
6.000
Initial stage
Equivalence point
4.000 stage VEP
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Volume (mL) NaOH
Four Stages of a Titration Reaction
Stage 1: Initial Stage (VT = 0)
Stage 2: Before The Equivalence

Point Stage
(0 < VT < VEP)
Stage 3: During The Equivalence

Point Stage
(VT = VEP )
Stage 4: After The Equivalence

Point Stage
(VT > VEP )
11
Stage 1: Initial Stage (VT = 0)
At this stage, only the analyte is present.
• The pH of the solution depends on the nature of the analyte
If the analyte is acidic, the pHSOLUTION is less than 7

If the analyte is basic, the pHSOLUTION is greater than 7
• GUIDE QUESTIONS:
Is the analyte acidic or basic?
Weak or strong?
Stage 2: : Before The Equivalence Point
Stage (0 < VT < VEP)
At this stage, the titrant is the limiting reagent while the

analyte is present in excess.
§ The amount of the product formed depends on the amount of the

titrant (limiting reagent)
§ The pH of the solution depends

on the nature of the product and
analyte present
§ GUIDE QUESTIONS:
What is the nature of the product
and reactant?
Stage 3: During The Equivalence Point Stage (VT = VEP )
A stoichiometric amount of the titrant has been added to the

solution.
The reaction is considered to be complete.
Only the product is present.
The pH of the titration

mixture: depends on the
product.
Stage 4: After The Equivalence Point Stage
(VT > VEP)
At this stage, the analyte is the limiting reactant

while the titrant is present in excess.
The amount of product depends on the amount of analyte
The pH of the solution depends

on the nature of the product and
the excess or unreacted titrant.
GUIDE QUESTIONS:
What is the nature of the
product and titrant?
Nature of the reacting species
Strong Acid (Analyte) - Strong Base (Titrant)
14.000
12.000
25.00 mL of 0.120 M HCl
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Volume (mL) NaOH
Strong Base (Analyte) - Strong Acid (Titrant)
Strong Base - Strong Acid Reaction
14.000
12.000
25.00 mL of 0.120 M NaOH
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00
Volume (mL) of 0.100 M HCl
Superimposed Titration Curves
Strong Acid (A)-Strong Base (T) and Strong Base (A) -Strong Acid (T)
14.000
12.000
10.000
8.000
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Vo l u m e ( m L) T
Weak Acid (Analyte) - Strong Base (Titrant)
Titration of 25.00 mL of 0.120 M Acetic acid with 0.100 M NaOH
14.000
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Weak Base (Analyte) - Strong Acid (Titrant)
Titration of 25.00 mL of 0.120 M NH3 with 0.100 M HCl
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Relationship between the pH break and the equilibrium
constant of the reaction
• The height of the pH break (distance between the two
parallel regions) is directly proportional to the KRXN
14.000
12.000
25.00 mL of 0.120 M HCl
10.000
8.000
pH break
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00
Volume (mL) NaOH
• Factors that affect the shape of the titration curve for acid-base
reactions: Limited to Reactions whose stoichiometric mole ratio
(SMR) between the analyte and the titrant is 1:1
Comparison Between the Titration Curves of a Strong
Acid vs a Weak Acid
Titration Curves of 25.00 mL of 0.120 M Strong Acid and Weak Acid
14.000
12.000
Unchanged
10.000
pH > 7
8.000
pH = 7
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Comparison Between the Titration Curves of a Strong
Acid vs a Weak Acid
Titration Curves of 25.00 mL of 0.120 M Strong Acid and Weak Acid
14.000
12.000
10.000
Height of the pH break (WA) is
shorter compared with the
8.000
Height of the pH break (SA)
pH
6.000
4.000
2.000
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Effect of Ka of the weak acids on the titration curve
As the Ka decreases (the relative strength of the weak acid
decreases) the height of the pH break decreases.
Titration of 2 Weak Acids
14.000
12.000
10.000
8.000
pH
6.000
4.000
2.000
0.000
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00
Volume (mL) Titrant
Effect of Concentration of the Analyte and Titrant
Figure A: Titration of 25.00 mL of 0.120 M HCl with 0.100 M NaOH
Figure B: Titration of 25.00 mL of 0.0120 M HCl with 0.0100 M NaOH
Effect of Concn on the Titration Curve
14.000
A The overall effect on

12.000
B
the titration curve:
10.000
The titration curve of

8.000
solution B is shorter
pH
6.000 than that of the

titration curve of the
4.000
B more concentrated
2.000 A solution A.
0.000
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00
Volume (mL) T
Guide to Titration Curve Problems
Step 1. Calculate the initial amount (mmol) of the

strong acid and the strong base.
Step 2. Identify the excess and the limiting reactants.
Step 3. Determine the amount (mmole) of the excess

reactant that will remain in the solution.
Step 4. Calculate the concentration of the excess

reactant and related this to the pH of the solution .
Exp’t. #3 – POTENTIOMETRY Methodology
• 0.100 M NaOH titrant was prepared and standardized

against KHP to the phenolphthalein endpoint in the
previous experiment (Exp’t 2).
• An unknown (weak) acid is loaded in the potentiometry
setup (25mL).
• Standard NaOH were added incrementally, and the pH
was measured after each addition. NaOH was added
until pH is around 10-11.
• Three trials were performed.
27
Exp’t. #3 – POTENTIOMETRY Calculations
28
Titration Plots and Equivalence point
• How is the endpoint estimated in titration curves?
Plot Veq
pH vs V Inflection point
1st Derivative Maximum/minimum
2nd Derivative X-intercept
29
Graphic Endpoint: Titration Curve
Graphic Endpoint: 1st derivative
Graphic Endpoint: 2nd derivative
POTENTIOMETRY Guides
• The importance of narrowing down the increments as the

equivalence point is reached.
- pH changes rapidly as equivalence point is reached, thus,
data points to describe that region of the curve are important
to enhance the constructed titration curve.
• The advantages and disadvantages of using potentiometric
titration.
Advantages: titration error is avoided and Veq determined is
more accurate. No indicator needed. Useful with
colored/turbid solutions
Disadvantages: time consuming and tedious, requires a lot of
data, and further data manipulation and plotting.
33
E3 – POTENTIOMETRY Calculations
• The equivalence point can be approximated in each plot

by inspection of key regions of the potentiometry plots.
• The pKa (and thus, the Ka), is estimated at half-
equivalence point, where log [A-]/[HA] vanishes
[base]
pH = pKa + log
[acid]
• Thus, at ½ VEP
pH = pKa
34
Graphic Endpoint: Titration Curve
½ VEP
Experiment #3 Data Sheet
Experiment #3 Data Sheet
Output:
• Prepare 3 potentiometric titration curves by plotting

pH against volume of base titrant.
• Identify the end point of the titration and the volume
(mL) of the titrant needed to reach the end point.
• Shade the area where the indicator end point occurred.
• Compare the pKa obtained from the two methods.
Check your experimental values with the value
obtained from the Table of the Acid Dissociation
Constant.
Titration of SA vs SB
HCl (aq) + NaOH (aq) ⟶ H2O (l) + NaCl (aq)
H+(aq) + OH-(aq) ⟶ H2O (l)
• Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH. Let us show calculation of

pH at VNaOH (mL) = 0.00, 5.00, 10.0, 25.0, 30.0 and 35.0.
Titration of 25.0 mL of .100 M HCl with 0.100 NaOH
1. Before titration: pH=?

MHCl=0.100M | VHCl=25.0 mL | VNaOH = 0.00 mL
39
2. Before Equivalence Point: pH=?

MHCl=0.100M * VHCl=25.0 mL | MNaOH = 0.100 M * VNaOH = 5.00 mL

Concentration (M)
0.100 0.100
Volume (mL) 25.0 5.00
Available (mmol) 2.50 0.500
Reacted (mmol) 0.500 0.500 Produced
0.500
Excess (mmol) 2.00 0.00
40


Concentration (M)
0.100 0.100
Volume (mL) 25.0 10.0
1.00
41
3. At the Equivalence Point: pH=?


Concentration (M)
0.100 0.100
Volume (mL) 25.0 25.00
2.500
42
4. After the Equivalence Point: pH=?


Concentration (M)
0.100 0.100
Volume (mL) 25.0 30.0
2.50
43


Concentration (M)
0.100 0.100
Volume (mL) 25.0 35.0
2.50
44
Titration of WA vs SB
CH3COOH (aq) + NaOH (aq) ⟶ CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) ⟶ CH3COO- (aq) + H2O (l)
• Titration of 25 mL of 0.100 M HAc (Ka=1.8x10-5) with 0.100 M NaOH. Let us

show calculation of pH at VNaOH (mL) = 0.00, 5.00, 10.0, 25.0, 30.0 and 35.0.
Titration of 25.0 mL of .100 M HAc with 0.100 NaOH

MHAc=0.100M | VHAc=25.0 mL | VNaOH = 0.00 mL
HAc (aq) + H2O (l) ⇌ Ac- (aq) + H3O+ (aq) Ka=1.8 x10-5
Initial 0.100 0 0
Change -x +x +x
Equilibrium 0.100 - x x x
46

MHAc=0.100M * VHAc=25.0 mL | MNaOH = 0.100 M * VNaOH = 5.00 mL
HAc (aq) + NaOH (aq) ⟶ NaAc (aq) + H2O (l)

Concentration (M) 0.100 0.100
Volume (mL) 25.0 5.00
mmol Available 2.50 0.500
mmol Reacted 0.500 0.500 0.500 Produced
mmol Excess 2.00 0.00
2. Before Equivalence Point: pH=? VNaOH = 5.00 mL

Initial 0
Change
Equilibrium
48

Using HHE
49


Volume (mL) 25.0 10.0
mmol Reacted 1. 00 1.00 1.00 Produced
50

Initial 0
Change
Equilibrium
51

Using HHE
52


Volume (mL) 25.0 25.0
53
3. At the Equivalence Point: pH=? VNaOH = 25.0 mL
Ac- (aq) + H2O (l) ⇌ HAc (aq) + OH- (aq) Kb=?

Initial 0 0
Change
Equilibrium
54


Volume (mL) 25.0 30.0
55


Volume (mL) 25.0 35.0
56
Titration of WB vs SA
HCl (aq) + NH3 (aq) ⟶ NH4Cl (aq) H+ (aq) + NH3 (aq) ⟶ NH4+ (aq)
NH4+ (aq) + H2O (l) ⇌ NH3 (aq) + H+ (aq)
• Titration of 25 mL of 0.100 M NH3 (Kb=1.8x10-5) with 0.100 M HCl. Let us show

calculation of pH at VHCl (mL) = 0.00, 5.00, 10.0, 25.0, 30.0 and 35.0.
Titration of 25.0 mL of .100 M NH3 with 0.100 HCl

MNH3=0.100M | VNH3 =25.0 mL | VHCl = 0.00 mL
NH3 (aq) + H2O (l) ⇌ NH4+ (aq) + OH- (aq) Kb=1.8 x10-5
Initial 0.100 0 0
Change -x +x +x
Equilibrium 0.100 - x x x
58

MNH3=0.100M * VNH3=25.0 mL | MHCl = 0.100 M * VHCl = 5.00 mL
NH3 (aq) + HCl (aq) ⟶ NH4+ (aq) + Cl- (aq)

Volume (mL) 25.0 5.00
59
2. Before Equivalence Point: pH=? VHCl = 5.00 mL

Initial 0
Change
Equilibrium
60

Using HHE
61


Volume (mL) 25.0 10.0
mmol Reacted 1. 00 1.00 1.00 Produced
62

Initial 0
Change
Equilibrium
63

Using HHE
64


Volume (mL) 25.0 25.0
65
3. At the Equivalence Point: pH=? VHCl = 25.0 mL
NH4+ (aq) + H2O (l) ⇌ NH3 (aq) + H3O+ (aq) Ka=?

Initial 0 0
Change
Equilibrium
66


Volume (mL) 25.0 30.0
67


Volume (mL) 25.0 35.0
68
Let’s try this . . .
1. Calculate the pH of a 25.00 mL of 0.120 M HCl.
2. Complete the tables representing the titration of 25.00 mL of

0.120 M HCl with 0.100 M NaOH.
Let’s try this…
continuation of #2
70
Let’s try this …
3. Calculate the pH of the mixture resulting from the reaction
between 25.00 mL of 0.140 M HCl and 25.00 mL of 0.180 M
NaOH.
71
4. How may mL of 0.1400 M HNO3 are needed to reach the
equivalence point 25.00 mL of 0.1200 M Ba(OH)2?
72
5. Calculate the pH of a 25.00 mL solution of 0.120 M
CH3COOH (Ka= 1.75 x 10-5)
73
6. Complete the tables representing the titration of 25.00 mL of 0.120 M CH3COOH
(Ka= 1.75 x 10-5) with 0.100 M NaOH.
74
continuation of #6
75
7. Calculate the pH of a 25.00 mL of 0.120 M NH3 (Kb=
1.76 x10-5)
76
8. Complete the tables representing the titration of 25.00 mL
of 0.120 M NH3 (Kb= 1.76 x10-5) with 0.100 M HCl.
77
continuation of #8
78
Titration Curves
Figure 9-3 Titration curves

and indicator transition
ranges for the analysis of
mixtures containing
hydroxide, carbonate, and
hydrogen carbonate ions.
9-79
9. Consider the acid dissociation constant of CH3COOH at 250C as 1.75
x10-5 and the base dissociation constant of NH3 at 250C as 1.76 x10-5.
Calculate the pH of the following mixtures:
a) 50.00 mL of 0.140 M CH3COOH and 25.00 mL of 0.120 M NaOH
b) 25.00mL of 0.0860 M CH3COOH and 30.00 mL of 0.120 M NaOH
c) 50.00 mL of 0.110 M NH3 and 30.00 mL of 0.120 M HCl
d) 30.00 mL of 0.0920 M NH3 and 20.00 mL of 0.140 M HCl
80
Let’s try this…
Describe the composition of the ff titration curves

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Acid-Base Titration:

with Sir Adolf

Start of titration Point of Slight excess of

• The end point is chosen so that it coincides or occurs as

• A sigmoidal curve, important

• Plot of some property of

• For acid-base reactions,

Sigmoidal curve or S curve:

Sigmoidal curve or S curve:

Titration Curve of 25.00 mL of 0.120 M HCl with 0.100 M NaOH

10.000 pH break or pH transition

A sudden change in the pH of

the solution causes the slope of

Titration Curve of 25.00 mL of 0.120 M HCl with 0.100 M NaOH

4.000 Inflection point

Stoichiometric mole ratio (SMR) between

Strong Acid-Strong Base Reaction

10.000 0 < VT < VEP

Stage 2: Before The Equivalence

Stage 3: During The Equivalence

Stage 4: After The Equivalence

• The pH of the solution depends on the nature of the analyte

If the analyte is acidic, the pHSOLUTION is less than 7

At this stage, the titrant is the limiting reagent while the

§ The amount of the product formed depends on the amount of the

§ The pH of the solution depends

A stoichiometric amount of the titrant has been added to the

The reaction is considered to be complete.

Only the product is present.

The pH of the titration

At this stage, the analyte is the limiting reactant

The amount of product depends on the amount of analyte

The pH of the solution depends

Strong Acid-Strong Base Reaction

25.00 mL of 0.120 M HCl

Strong Base - Strong Acid Reaction

25.00 mL of 0.120 M NaOH

Titration of 25.00 mL of 0.120 M Acetic acid with 0.100 M NaOH

Titration of 25.00 mL of 0.120 M NH3 with 0.100 M HCl

25.00 mL of 0.120 M HCl

Titration Curves of 25.00 mL of 0.120 M Strong Acid and Weak Acid

Titration of 2 Weak Acids

Figure B: Titration of 25.00 mL of 0.0120 M HCl with 0.0100 M NaOH

Effect of Concn on the Titration Curve

A The overall effect on

The titration curve of

6.000 than that of the

Step 1. Calculate the initial amount (mmol) of the

Step 2. Identify the excess and the limiting reactants.

Step 3. Determine the amount (mmole) of the excess

Step 4. Calculate the concentration of the excess

• 0.100 M NaOH titrant was prepared and standardized

• How is the endpoint estimated in titration curves?

1st Derivative Maximum/minimum

2nd Derivative X-intercept

• The importance of narrowing down the increments as the

• The equivalence point can be approximated in each plot

• Prepare 3 potentiometric titration curves by plotting

• Titration of 25 mL of 0.100 M HCl with 0.100 M NaOH. Let us show calculation of