Course Name:: Volumetric and Gravimetric Analytical Chemistry: 4022133-3

Course Name: Volumetric and Gravimetric
Analytical Chemistry
Course Code: 4022133-3

Lecture 7 contents
Blank titration
Polyprotic acid
Acid-Base Titrations
• Strong acid with strong base
• Weak acid with strong base
Titration of strong acid with strong base
• The chemical reaction between titrant and analyte is:
H+ + OH-  H2O
• We have three region in the titration curve that represents
three different kinds of calculations:
1- Before reaching the eq. point:

the pH is determined by excess H+ in the solution
H+ + OH-  H2O + H+
much little excess
2- At the eq. Point:
the pH is determined by the dissociation of water
H2O  H+ + OH-
3- After the eq. Point:
the pH is determined by the excess OH- in the solution
H2O + OH-  H2O + OH-
excess
Example (1):
consider the titration of 50.0 mL of 0.100 M HCl using
a titrant of 0.200 M NaOH.
Step1:Calculate the volume of NaOH needed to reach the
equivalence point
moles ofClH= moles ofaOH
N
Ma.Va = Mb.Vb
‘a’ indicates the acid, HCl, and ‘b’ indicates the base, NaOH
Veq =Vb =VaMa = (0.100M

)(50.00ml
) = 25.00ml
Mb 0.200M
Step 2: Before adding the titrant, the pH is determined by

the analyte, which in this case is a strong acid.
At the start of the titration the solution is 0.100 M HCl,

because HCl is a strong acid, means that the pH is
pH = − log[ H ] = − log[ HCl ] = − log( 0 .100 ) = 1 .00

+
Step 3: Calculate pH values before the equivalence

point by determining the concentration of
unreacted analyte.
Before the equivalence point, HCl is present in excess and
the pH is determined by the concentration of unreacted
HCl.
After adding 10.0 mL of NaOH the concentration of
excess HCl is
the pH increases to 1.30

Step 4: calculate the pH at the equivalence point for

the titration of a strong acid with a strong base.
At the equivalence point the moles of HCl and the

moles of NaOH are equal. Since neither the acid nor
the base is in excess, the pH is determined for the
produced salt (salt of strong acid with strong base).
+ − + 2
K = [ H O ][OH ] = [ H 3 O ] = 1.00 X 10 − 14
w 3
[ H 3 O + ] = 1.00 X 1 0 − 7
the pH at the equivalence point is 7.00.

Step 5: Calculate pH values after the equivalence point by

determining the concentration of excess titrant.
For volumes of NaOH greater than the equivalence

point, the pH is determined by the concentration of
excess OH–.
After adding 30.0 mL of NaOH the concentration of

excess NaOH is
pOH = -Log [OH-] = -Log0.0125 = 1.90
pH =14-pOH = 12.10
Table1:Titration of 50.0 ml of HCl with 0.200M NaOH
Titration curve for the titration of 50.0 mL of 0.100 M HCl
with 0.200 M NaOH.
The red points correspond to the data in Table 1 . The blue
line shows the complete titration curve.
Example
Calculate the pH during the titration of 50.00 mL of 0.0500 M
NaOH with 0.1000 M HCl at 25°C after the addition of the
following volumes of reagent:
(a) 24.50 mL, (b) 25.00 mL, (c) 25.50 mL.
(a)
Example
Titration of weak acid with strong base
Example (1):
Consider the titration of 50.0 mL of 0.100 M acetic acid
CH3COOH using a titrant of 0.200 M NaOH. (Ka =
1.75x10-5 )
Step1:Calculate the volume of NaOH needed to reach the
equivalence point
Moles of CH3COOH = moles of NaOH
Ma x Va = Mb x Vb
‘a’ indicates the acid, CH3COOH, and ‘b’ indicates the base, NaOH
Veq =Vb = VaMa (0.100M

= )(50.00ml
) = 25.00ml
Mb 0.200M
Step 2: Before starting titration (before adding the titrant),

the pH is determined by the analyte, which in this case is a
weak acid.
-Before adding NaOH the pH is that for a solution of 0.100 M
acetic acid.
-Because acetic acid is a weak acid,
CH3CCOH (aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

[H3O+] =[H+] = ka[acid]
pH= -Log [H+] = - Log 1.75 x10-5 x 0.1 =2.88
At the beginning of the titration the pH is 2.88.

Step 3: Before the equivalence point, the pH is determined
by a buffer containing the analyte and its conjugate form.
Before the equivalence point the concentration of unreacted

acetic acid is
and the concentration of acetate is

After adding 10.0 mL of NaOH the concentrations of

CH3COOH and CH3COO– are (buffer solution)
They form buffer

solution
pH = pKa + log [salt]

[acid]
How to calculate the

pH of a buffer solution
Step 4: The pH at the equivalence point is determined by the

analyte΄s conjugate form, which in this case is a weak base
-At the equivalence point the moles of acetic acid initially

present and the moles of NaOH added are identical.
- Because their reaction effectively proceeds to
completion, the predominate ion in solution is CH3COO–,
which is a weak base.
-To calculate the pH we first determine the concentration of

CH3COO–
we calculate the pH of the produced salt (salt of week
acid and strong base)
[H+]= Kw.Ka
Csalt
[H+]= 10-14 X 1.75 x10 -5 /0.0667 = 1.62 x 10-9
pH = -Log [H+] = -Log 1.62 x 10-9
pH at the equivalence point is 8.79.

Step 5: Calculate pH values after the equivalence point
by determining the concentration of excess titrant.
-After the equivalence point, the titrant is in excess and the

titration mixture is a dilute solution of NaOH.
-We can calculate the pH using the same strategy as in the

titration of a strong acid with a strong base.
after adding 30.0 mL of NaOH the concentration of

OH– is
poH = -Log [OH-] = -Log0.0125 = 1.90
pH =14-pOH = 12.10
Table2: Titration of 50.0 mL of 0.100 M
Acetic Acid with 0.200 M NaOH
Titration curve for the titration of 50.0 mL of 0.100 M
CH3COOH with 0.200 M NaOH. The red points
correspond to the data inTable 2. The blue line shows
the complete titration curve.
Homework
Calculate the pH at 0, 10, 25, 50, 60 and 80 ml titrant, in the

titration of 50 ml of 0.1M CH3COOH with 0.1M NaOH.

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Course Name: Volumetric and Gravimetric

Course Code: 4022133-3

1- Before reaching the eq. point:

Veq =Vb =VaMa = (0.100M

Step 2: Before adding the titrant, the pH is determined by

At the start of the titration the solution is 0.100 M HCl,

pH = − log[ H ] = − log[ HCl ] = − log( 0 .100 ) = 1 .00

Step 3: Calculate pH values before the equivalence

the pH increases to 1.30

Step 4: calculate the pH at the equivalence point for

At the equivalence point the moles of HCl and the

the pH at the equivalence point is 7.00.

Step 5: Calculate pH values after the equivalence point by

For volumes of NaOH greater than the equivalence

After adding 30.0 mL of NaOH the concentration of

pOH = -Log [OH-] = -Log0.0125 = 1.90

Veq =Vb = VaMa (0.100M

Step 2: Before starting titration (before adding the titrant),

CH3CCOH (aq) + H2O(l) H3O+(aq) + CH3COO-(aq)

[H3O+] =[H+] = ka[acid]

pH= -Log [H+] = - Log 1.75 x10-5 x 0.1 =2.88

At the beginning of the titration the pH is 2.88.

Before the equivalence point the concentration of unreacted

and the concentration of acetate is

After adding 10.0 mL of NaOH the concentrations of

They form buffer

pH = pKa + log [salt]

How to calculate the

Step 4: The pH at the equivalence point is determined by the

-At the equivalence point the moles of acetic acid initially

-To calculate the pH we first determine the concentration of

[H+]= 10-14 X 1.75 x10 -5 /0.0667 = 1.62 x 10-9

pH = -Log [H+] = -Log 1.62 x 10-9

pH at the equivalence point is 8.79.

-After the equivalence point, the titrant is in excess and the

-We can calculate the pH using the same strategy as in the

after adding 30.0 mL of NaOH the concentration of

poH = -Log [OH-] = -Log0.0125 = 1.90

Calculate the pH at 0, 10, 25, 50, 60 and 80 ml titrant, in the

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