CHM 1046: General Chemistry and

Qualitative Analysis

Unit 19
Acid Base Equilibria:
Titrations
Dr. Jorge L. Alonso Textbook Reference:
Miami-Dade College – •Chapter 19 (sec. 5-8)
Kendall Campus •Module 9
Aqueous
Equilibria

Miami, FL
•Soln-Unknown
Concentration (M): Acid
Titration
A volumetric
• Known
•Standard-of known Conc.(M) technique in which
Volume one can determine
(V) the concentration
•Measure Vol to reach end pt.
of a solute in a
MolesB = M x V solution of
 
   L unknown
 L
concentration, by
making it react
MolesA = M x V
with another
solution of known
concentration
(standard).
Aqueous
If: MolesA = MolesB Equilibria
{*TitrationMovie} Then: (M x V)A = (M x V)B
Determining the Concentration of
Solutions by Titration
A known concentration of
base (or acid) is slowly added to
a solution of acid (or base) until
neutralization occurs.
(Standard)
Example:
HCl (aq) + NaOH (aq)  NaCl (aq) + H2O (l)
xa HA (aq) + xb MOH (aq)  MA (aq) + H2O (l)
H2SO4(aq) + 2NaOH(aq)  Na2SO4(aq) + H2O(l)
Neutralization: equivalence point

 1 H 2SO 4 
# mol1(acid) = # mol2(base) ? H 2SO 4  1NaOH Aqueous 
Equilibria
2 NaOH 
1 mol1(acid) = 1 mol2(base)
xa xb
 Titration Calculations:
Stoichiometry using Molarities
xA HN + xB MOH  MN + HOH
Neutralization: 1 moles(acid) = 1 moles(base)
xA xB
Since moles = MV = moles x Liter
Liter
 # g 
 # g


MW  ηA MA x V A MB x V B ηB  MW 
= = = = =
xA xA xA xB xB xB
Where x A or B = coefficients from balanced equations
Aqueous
* Equation Useful for determining Molarities and Equilibria
Volumes at the Equivalence Point of a Titration *
 Solution Stoichiometry Problems:
Molarity
Problem: A volume of 16.3 mL of a 0.30M NaOH solution was
used to titrate 25.00 mL H2SO4. What is the concentration of
H2SO4 in the solution of unknown concentration?

H2SO4 + 2 NaOH  2HOH + Na2SO4

MA x VA = MB x VB
x1A xB
2

1M B VB 1  0.30M 16.3 mL

MA   = 0.098 M H2SO4
2 VA 2  25.00 mL
Aqueous
Titration of a Strong Acid with a Strong Base Equilibria
 Titration Graph: pH vs. Volume

Titration
Data: Excess base
mL of pH
NaOH
SB
0 1.2
10 1.4 Phenolphthalein Indicator
20 1.6
30 1.7 Acid = Base
40 1.9 Methyl Red Indicator
50 7.0
60 12.0
pH
70 12.2 meter
12.3
Excess acid
80
SA Aqueous
Equilibria
{Titration2}
 Titrations: The Strength of
Acids & Bases
Strong Base with Strong Weak Base with Strong Acid
SA Acid SA
Phenolphthalein

8-10

SB WB

Strong Base with Weak Acid Weak Base with Weak Acid
WA WA

Aqueous
Equilibria
SB WB
(2) Titration of a WA with a SB

With weaker acids,

the initial pH is
higher and pH
changes near the
equivalence point
are more subtle.

Aqueous
Equilibria
 Selecting Appropriate Indicators
Select appropriate indicator for following:

Phenolph

Meth Red Meth Red

Phenolph
?????

• an indicator is chosen so that it will change color at a pH just beyond the

equivalence point (mid point of the steep vertical portion of the graph). The
first point at which the indicator permanently changes color marks the end of
the titration and is called the indicator end-point. Dropping a perpendicular
Aqueous
from the indicator end-point to the x-axis is a very close estimation ofEquilibria
the
equivalence point.
SB (1) Titration of a SA with a SB SA

(or SB with a SA)

SA SB

Aqueous
Equilibria
 Acid-Base Neutralization Equations
(1) Strong Acids and Bases are represented in completely dissociated state:
as H+ and OH-

(2) Weak Acids and Bases are represented in undissociated state:

as HA and B (or MOH)

Aqueous
Equilibria
(H2CO3 + K+)

(H2CO3 + Ca2+ + C2H3O2- )

(H2C O3 + Zn2+)

(H2CO3 + Zn2+ + SO42-)

Aqueous
Equilibria
 Equations and Tables used in
solving A-B Titration Problems
(1) Acid Base Neutralization: when you  MV  A   MV  B
reach the end-point using SA or SB A B

(2) Acid Base Neutralization: when not (3) WA or WB Equilibrium

at the end-point or using WA or WB problems
HA ↔ H+ + A-
HA + OH-  H2O + A- KA 
[ H  ][ A  ] [ A ]
[ HA] pH  pK a  log
[ HA]

Use: Mole ICEnd Table Use: [ICE] Table

Mole HA + MOH → MA + H20 HA ↔ H+ A-
(.15M)(.025L) (.10M)(.030L)
II 0.061 0 0
II 0.0038 η 0.0030 η 0 η Aqueous
C -x +x
C - 0.0030 η - 0.0030 η + 0.0030 η Equilibria +x
E 0.061 - x x x
End 0.0008 η 0 η 0.0030 η
 (1) Titration of a SA with a SB
Example: 25 mL of 0.15M HCl with 0.10M NaOH.
(1) What volume of NaOH is required to reach the equivalence point?
 A B
 VB 
 MV  A B
 A B A MB
 MV  A   MV  B  0.15M  .025L  (1)
VB   37.5mL
A B (1)  0.10 M 
(2) What is the pH of the initial strong acid? (strong acid problem)
In strong acid [HA]=[H+], so pH=-log [H+] = -log (0.15) = 0.82
(3) What is the pH prior to the equivalence point? Let’s say after 30. mL of
NaOH. (excess SA problem) *what is used for neutralization Rx?*
 (0.0008)
Mole HX + MOH → MX + H20
[ HX ]  [ H  ]  
(.15M)(.025L) (.10M)(.030L) L (.025L  .030L)
II 0.0038 η 0.0030 η 0
C - 0.0030 η - 0.0030 η + 0.0030 η [ H  ]  1.4  102 M
End 0.0008 η 0 0.0030 η Aqueous
pH = -log (1.4 x 10-2) = 1.9
Equilibria
Salt of SA & SB:
will not Hydrolyze
 (1) Titration of a SA with a SB
Example: 25 mL of 0.15M HCl with 0.1M NaOH.
(4) What is the pH at the equivalence point?
Only salt + water present and salt will not hydrolyze water since it is
derived from SA & SB. So pH = 7

(5) What is the pH after the equivalence point? Lets say after 40. mL of
NaOH. (excess SB problem) *what is used for neutralization Rx?*
mole HX + MOH → MX + H20
(.15M)(.025L) (.10M)(.040L)
II 0.0038 η 0.0040 η 0 η
C - 0.0038 η - 0.0038 η + 0.0038 η
Salt of SA & SB:
End 0η 0.0002 η 0.0038 η will not Hydrolyze

0.0002
[OH  ]   3.110 3 M pOH = -log(3.1x10-3) = 2.5
(.025 L  .040 L)
pH + pOH = pKw pH = pKw - pOH Aqueous
Equilibria
pH = 14 – 2.5 = 11.5
 (2) Titration of a WA with a SB
SB (OH-)
HA ↔ H+ + A-
HA + OH-  H2O + A-
*what is used for neutralization Rx?*

• Unlike in the previous [ H  ][ A  ]

KA 
case, the conjugate base [ HA]
of the acid affects the pH
when it is formed.
[ A ]
pH  pK a  log
• The pH >7 at the [ HA]
equivalence point.

Aqueous
Equilibria
*what is used for equilibrium Rx?*
 (2) Titration of a WA with a SB
Example: 25 mL of 0.15M HC2H3O2 (Ka= 1.8 X10-5) with 0.10M NaOH.
(1) What volume of NaOH is required to reach the equivalence point?
 A B
 VB 
 MV  A B
 A B A MB
 MV  A   MV  B  0.15M  0.025L  (1)
VB   37.5mL
A B (1)  0.10M 
(2) What is the initial pH of the acetic acid? (Before titration, WA
Equilibrium
 
problem)
[ H ][ A ]
+ -
HA ↔ H A
K a II 0.15 0 0
[ HA]
C -x +x +x
( x)( x )
1.8  10 5  E 0.15 - x x x
(0.15  x)
Aqueous
x 2  (1.8 10 5 )(0.15)  2.7 10 6 pH   log(0.0016)  2.8 Equilibria
x  [ H  ]  0.0016
 (2) Titration of a WA with a SB
Example: 25 mL of 0.15M HC2H3O2 (Ka= 1.8 X10-5) with 0.10M NaOH.
(3) What is the pH prior to the equivalence point? Let’s say after 30. mL
of NaOH. (WA Buffer problem)

mole HA + MOH → MA + H20

(.15M)(.025L) (.10M)(.030L)
II 0.0038 η 0.0030 η 0 η
C - 0.0030 η - 0.0030 η + 0.0030 η
Salt of WA & SB:
End 0.0008 η 0 η 0.0030 η WILL Hydrolyze H2O

(0.0008 ) (0.0030 )
[ HA]   0.015M [ A ]   0.055M
 0.025L  0.030L   0.025L  0.030 L 
[ A ]
pH  pK a  log  pK a  log[ A ]  log[ HA]
[ HA]
Aqueous
pH   log(1.8 105 )  log(0.055)  log(0.015)  (4.7)  (1.3)  (1.8)  5.2 Equilibria
 (2) Titration of a WA with a SB

Example: 25 mL of 0.15M HC2H3O2 (Ka= 1.8 X10-5) with 0.1M NaOH.

(4) What is the pH at the equivalence point? This happens @ 37.5 mL
(Hydrolysis of Salt derived from a WA & SB)

mole HA + MOH → MA + H20

(.15M)(.025L) (.10M)(.038L)
II 0.0038 η 0.0038 η 0 η
C - 0.0038 η - 0.0038 η + 0.0038 η
Salt of WA & : will
End 0η 0 η 0.0038 η Hydrolyze water

Salt is NaC2H3O2

Na+ = derived from SB (NaOH), will not hydrolyze.

C2H3O2- = derived from WA (acetic acid) it WILL hydrolyze water.
Aqueous
Equilibria
 (2) Titration of a WA with a SB
Example: 25 mL of 0.15M HC2H3O2 (Ka= 1.8 X10-5) with 0.1M NaOH.
(4) What is the pH at the equivalence point? This happens @ 37.5 mL
(Hydrolysis of Salt derived from a WA & SB)
mole HA + MOH → MA + H20
(.15M)(.025L) (.10M)(.038L)
0.0038
II 0.0038 η 0.0038 η 0 η
[C2H3O2-] =.  0.066M
C - 0.0038 η - 0.0038 η + 0.0038 η (.025L  .038L)
End 0η 0 η 0.0038 η Salt is NaC2H3O2

C2H3O2- + H2O ↔ HC2H3O2 + OH-

II 0.061 0 0
C -x +x +x
K w  Ka  Kb E 0.061 - x x x

K w 1.0 10 14 [ HA][OH  ] ( x)( x)

K b   5 . 6  10 10 K b 
 5.6  10 10

K a 1.8  10 5 [A ] (0.061  x)
x 2  (5.6  10 10 )(0.066)  3.7 10 11
Aqueous
pH + pOH = pKw pH = pKw - pOH 
x  [OH ]  6.1 10 6
Equilibria

pH = 14 – 5.2 = 8.8 pOH   log(6.110 6 )  5.2

2005B Q1

Aqueous
Equilibria
Mole ICEnd Table:

Aqueous
Equilibria
 (3) Titration of a WB with a SA

SA (H3O+)

MOH ↔ M+ + OH-
H3O+ + MOH  2H2O + M+

• The pH at the
equivalence point
in these titrations
is < 7.
• Methyl red is the
indicator of Aqueous
choice. Equilibria
 (3) Titration of a WB with a SA:
Calculation of pH
(1) Acid Base Neutralization (2) WB Equilibrium problem
B+ H2O ↔ BH+ + OH-
- [ BH  ][OH  ]
B + H+  H2O + A KB 
[ B]
[ BH  ]
pOH  pK B  log
[ B]

Weak base and

strong acid

Use: Mole ICEnd Table Use: [ICE] Table

Mole B + H+ → A- + H20 B + H2O BH+ OH-
(.15M)(.025L) (.10M)(.030L)
↔
II 0.061 0 0
II 0.0038 η 0.0030 η 0 η Aqueous
C -x +x
C - 0.0030 η - 0.0030 η + 0.0030 η Equilibria +x
E 0.061 - x x x
End 0.0008 η 0 η 0.0030 η
2007A Q1 Titration: weak acid with strong base

Aqueous
Equilibria
 Use: Mole ICEnd Table
Mole HA + OH- → A- + H20
(.40 M)(.025L) (.40M)(.015L)

II 0.010 η 0.0060 η 0 η

C - 0.0060 η - 0.0060 η + 0.0060 η

End 0.0040 η 0 η 0.0060 η

(e) What’s pH? solu (0.006)

For F-: M   = 0.15 M F
-
Lso ln (0.015  0.025) L
Aqueous
solu (0.004)
For HF: M   Equilibria
= 0.10 M HF
Lso ln (0.015  0.025) L
 0.15 M F-
0.10 M HF
Use: [ICE] Table
HA H+ ↔ A-

II 0.10 0 0.15
C -x +x +x
E 0.10 - x x 0.15 + x

Aqueous
Equilibria
Titrations of Polyprotic Acids
Ka3

In these
cases there is
an
Ka2 equivalence
point for each
dissociation.

Ka1

Aqueous
Equilibria
2005B Q1
Titration: weak
acid strong base

Aqueous
Equilibria
2005B Q1

Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
Equilibria
2000 QA Titration: weak
base strong acid

Aqueous
Equilibria
Aqueous
Equilibria
Titration: weak
2001 Q3
acid strong base

Aqueous
Equilibria
Answers 2001 Q3

Aqueous
Equilibria
2002A Q1 Titration: weak
acid strong base

Aqueous
Equilibria
Aqueous
Equilibria
2003A Q1 Titration: weak
base strong acid

Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
Equilibria
2006B Q1 Titration: weak
acid strong base

Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
Equilibria
 Expressing
Concentrations of
Solutions:
Molarity (& Normality*)
Aqueous
* For MDC students only! Equilibria
 moles of solute
Molarity (M) =
Liters of solution

xA HN + xB MOH  MN + HOH
mol A mol B
xA = xB

(mol/L)A x LA (mol/LB) x LB
xA
= xB

MA x VA = MB x VB
xA xB
Aqueous
Where x A or B = coefficients for the acid (A) and the base (B) Equilibria
from the
balanced neutralization equations
 mol A mol B
xA = xB

(mol/L)A x LA (mol/LB) x LB
xA
= xB

MA x VA xA M x VB
= B
xB

molesA xA MB x VB
= xB
Aqueous
Equilibria
 xA HN + xB MOH  MN + HOH
For titrations:

Since
 1 mole 
molesA  # g solute A  
 g - MM A 

 # g solute 
xA MB x VB
Aqueous

 g - MM 

= xB Equilibria
Lesson for MDC students only:
Molarity (M) vs. Normality (N)
mol of solute equiv of solute
M= N=
L of solution L of solution

 1 mole   1 mole 
moles  # g Solute   equivalents  # g Solute  
 g - EW 
 g - MM 
g - MM
g - EW 
n
Where:
M=N
When n = 1 n A/B = # H +
or #OH -

That is when using HCl, KHP NaOH

But not when using H2SO4, Ca(OH)2
n Redox = #e -
involved in Aqueous
balanced
Equilibria

redox equation.
 Molarity (M) vs. Normality (N)

Acid g-MM (g/) Molarity (/L) Normality (eq/L)

+ H20 to g-EW Eq(g/gEW)
HCl 36 g + 1L = 1M = 1N 36/1 36/36
=36
H2SO4 98 g + 1L = 1M = 2N 98/2 98/49
=49
H3PO4 98 g + 1L = 1M = 3N 98/3 98/33
=32.7 Aqueous
Equilibria
2H3PO4 + 3 Ca(OH)2  6 HOH + Na3PO4

2M H3PO4 3M Ca(OH)2 Using Molarity

1N H3PO4 1N Ca(OH)2 Using Normality

N = nM or M = N
n

Using Normality for titrations:

NA x VA = NB x VB Aqueous
Equilibria
 Titration of a WA with a SB
• Unlike in the previous
case, the conjugate
base of the acid affects
the pH when it is formed.

• The pH at the
equivalence point will
be >7.
• Phenolphthalein is
commonly used as an
indicator in these
titrations.

Aqueous
Equilibria
 Titration: measuring the
+ -
Equivalence Point (H = OH )

Methyl red Phenolphthalein

in base in base
(range R4-6Y) (range C 8-10 F)

A pH meter or indicators are used to determine when the

solution has reached the equivalence point, at which the
Aqueous
stoichiometric amount of acid equals that of base. The end-
Equilibria

point of a titration is when indicator changes color.

 Titration of a SA with a SB
xA HN + xB MOH  MN(aq) + HOH
1. From the start of the titration
the pH goes up slowly. Just
before the equivalence point,
the pH increases rapidly. Excess base

2. At the equivalence point,

moles H+ = moles OH-,
and the solution contains
only water and the salt
from the cation of the base
and the anion of the acid. H+ = OH-

3. Just after the equivalence

point, the pH increases
rapidly. As more base is
added, the increase in pH Excess acid Aqueous
Equilibria
again levels off.
 Solution of unknown
Titration Solution of known
concentration
concentration (M2 x V2 = #mol2)
(M1 x V1 = #mol1)

Aqueous
Equilibria
Neutralization: 1 mola = 1 molb
{*TitrationMovie} (equivalence point) xa xb
Stoichiometric/Volumetric Calculations
xA HN + xB MOH  MN + HOH

ACID ACID ACID

xA

xB

BASE BASE BASE

 #g   #g 

 MW

A MA x VA MB x VB  
 MW Aqueous
= =
B
= xB Equilibria
xA xA xB
2006 (B)

Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
Equilibria
2007 (A)

Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
Equilibria
Aqueous
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Equilibria
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