Tadeusz Grecki

Ionic Equilibria

Acid-Base Equilibria
Brnsted-Lowry: an acid is a proton _______, a base is a ______________.
Acid Base + H +

________________ (H3PO4, H2O), ______ ( NH 4+ ) and _____ (H2PO4-) can all

behave as acids.
Example:
NH 4+ NH 3 + H +
Substances which can behave both as acids and as bases: ____________, or
______________ substances (e.g. H2O, SH-).

SH H + + S 2
acid

base

H + + SH H 2 S
base

acid

Free protons _________ in any solvent, thus the above reactions are
______________. In reality:
NH 4+ + H 2O NH 3 + H 3O +
Energy required to dissociate _____ to ____ and __: _____ kcal/mol

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Tadeusz Grecki

Ionic Equilibria

Equilibrium constant for _______________:

HA + H 2O H 3O + + A
[ H + ][ A ]
Ka =
[ HA]
________________:
B + H 2O BH + + OH

[ BH + ][OH ]
Kb =
[ B]
Relationship between Ka and Kb:
K a Kb = K w
Ka =

Kw
Kb

Kb =

Kw
Ka

Lewis: an acid is an ___________________; a base is an _________________.

________________________________________________________________
Strength of acids and bases
HSO4 + H 2O H 3O + + SO42
H 2CO3 + H 2O H 3O + + HCO3
HCN + H 2O H 3O + + CN
acid1 + base2 acid 2 + base1
[ H 3O + ][ SO42 ]
= _______
Ka =
[ HSO4 ]
[ H 3O + ][ HCO3 ]
Ka =
= _______
[ H 2 CO3 ]
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Tadeusz Grecki

Ionic Equilibria

[ H 3O + ][CN ]
Ka =
= ______
[ HCN ]
_______ value of __ means that the acid is ________, thus:
______________________
____________ of water:
H 2O H + + OH

Equilibrium constant using __________:

K0 =

a H + aOH
a H 2O

Activity of water is by thermodynamic convention proportional to the ____

_________ of water in the solution. In dilute solutions it is close to __.
Activity of water can be _____________________:

a H aOH = [ H + ] + [OH ] = ___

+

"________________" constant:
[ H + ][OH ] = K w
Kw = K 0

aH 2O

= K w0 / +

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Tadeusz Grecki

Ionic Equilibria

At 50C, pKw = ______, and the neutral point is pH = ____. At 25C in 3 M

NaClO4 pKw = _____, and the neutral point is pH = ____.

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Tadeusz Grecki

Ionic Equilibria

____________ solvents:
NH 3 + NH 3 NH 4+ + NH 2
At -60C, the equilibrium constant is:
K = [ NH 4+ ][ NH 2 ] = 10 32

Thus, the pH scale (defined as -log[NH4+]) in liquid ammonia ranges from _ to

__.

pH of a strong acid
Initially PH, or "_________________", defined as
PH = -log CH
Today's definition of pH:
pH = pa H = log a H = log([ H + ] + )

General approach
Example: HCl
Mass balance:
Ion product of water:
Charge balance:

Solution:

[Cl ] = ____
[ H + ][OH ] = K w = ____
[ H + ] = [OH ] + [Cl ]

[H + ] =

Kw
+ C HA
[H + ]

This is a quadratic equation, which applies ________.

When ____________, [H+] = ___ ([OH-] is _______________)
At higher ionic strength, activity coefficient should be used.
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Tadeusz Grecki

Ionic Equilibria

Strong base:
Example: NaOH

[ Na + ] = ___

Mass balance:
Ion product of water:
Charge balance:

[ H + ][OH ] = K w = 1014
_____________________

Solution:

[ H + ] + Cb =

Kw
[H + ]

Basic solution, thus ______________, and in general

[H + ] =

Kw
Cb

___________________
____________________________________
Example: pH of 2 107 M solution of NaOH
[ H + ]2 + Cb [ H + ] K w = 0
Cb + Cb2 + 4 K w
[H ] =
2
+

[ H + ] = 4.14 10 8 mol / L

Simplified equation: pH = _____

____________________________________

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pH = _____

Tadeusz Grecki

Ionic Equilibria

pH of strong acid/base as a function of concentration:

log C

0
0
-1
-2
-3
-4
-5
-6
-7
-8
-9
-10

10

log C(acid)

12

log C(base)

pH

Mixture of a strong acid and a strong base

Example: HCl and NaOH
Mass balance:
Mass balance:
Ion product of water:
Charge balance:

[Cl ] = ___
[ Na + ] = ___
[ H + ][OH ] = K w = 1014
[ H + ] + [ Na + ] = [Cl ] + [OH ]

C a Cb = [ H + ]

Kw
[H + ]

When the acid and the base are ____________:

[ H + ] = [OH ] = K w = 10 7 mol / L

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Ionic Equilibria

Titration of Strong Acids and Bases

Volume of the system changes, thus _______ must be taken into mass balances
rather than _______________.
Example: titration of HCl with NaOH:

[Cl ](Va + Vb ) = ________

[ Na + ](Va + Vb ) = ________

Mass balance:
Mass balance:
Ion product of water:
Charge balance:

[ H + ][OH ] = K w = 1014
[ H + ] + [ Na + ] = [Cl ] + [OH ]

[H + ] +

CbVb
CV
K
= a a + w+
Va + Vb Va + Vb [ H ]

At the equivalence point, __________ (1:1 stoichiometry) and ___________

Before the equivalence point, _______________:

[H + ] =

CaVa CbVb
Va + Vb

After the equivalence point, _______________:

Kw
CbVb CaVa
=
Va + Vb
[H + ]

[H + ] =

K w (Va + Vb )
CbVb CaVa
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Tadeusz Grecki

Ionic Equilibria

In the vicinity of the equivalence point (Ca = 0.1 M, Va = 50 mL, Cb = 0.2 M):
9

pH 7

OH- neglected
Full equation
H+ neglected
6

5
24.999

24.9995

25

25.0005

Vb

Plotting the titration curve

__________ titrated with _________:
Ca [ H + ] + K w /[ H + ]

Vb = Va
+
+
Cb + [ H ] K w /[ H ]

Titration of ___________ with ___________:

Cb + [ H + ] K w /[ H + ]

Va = Vb
+
+
Ca [ H ] + K w /[ H ]

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25.001

Tadeusz Grecki

Ionic Equilibria

Example:
Titration curve

14

12

10

pH

0
0

10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50

Vb

_______________ titration:
HCl titrated with NaOH
= H [ H + ] + Na [ Na + ] + OH [OH ] + Cl [Cl ]
- _______ conductance ( [k 1cm 1 ] )
X - __________ conductance.
At 25C, ________ conductances 0 are:
H + 0 = _____
Na + 0 = _____
OH 0 = _____
Cl 0 = _____

Procedure:

______ the values of pH;

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Tadeusz Grecki

Ionic Equilibria

________ [H+] and [OH-];

calculate V from the ____________ equation;
calculate [ Na + ] = CbV /(V + V0 ) (from ___________);

calculate [Cl ] = CaV0 /(V + V0 ) (from ___________).

50 mL 0.1 M HCl titrated with 0.2 M NaOH:

35

30

Conductance

25

20

15

10

0
0

10

20

30

40

50

Vb

50 mL 0.0001 M HCl titrated with 0.0001 M NaOH:

0.011
0.0105
0.01

Conductance

0.0095
0.009
0.0085
0.008
0.0075
0.007
0.0065
0.006
40

50

Vb

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Tadeusz Grecki

Ionic Equilibria

Titration error
Titration error =

Vep V '
V'

Vep - V at ________
V' - V at _______________
Titration of 50 mL 0.1 M HCl with 0.2 M NaOH:

Enlarged section (end point detected with __________ at pH = 5):

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Tadeusz Grecki

Ionic Equilibria

Titration error:
100

24.9963 25
= _________
25

________________
50 mL 0.0001 M HCl titrated with 0.0001 M NaOH:

Titration error:
100

40 50
= ______
50

Gran plots
Titration of a ___________ with a __________:
[H + ] +

CbVb
CV
K
= a a + w+
Va + Vb Va + Vb [ H ]

Before the equivalence point, ______ is negligibly small, thus:

(Va + Vb )[ H + ] = CaVa CbVb
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Tadeusz Grecki

or

Ionic Equilibria

f1 = (Va + Vb )10 pH = CaVa CbVb

__ , ___ and __ are _________, thus a plot of f1 as a function of Vb should be a

____________ with a slope of _____ intersecting the X axis at the __________
_____, _____________.
Example: 50 mL 0.0001 M HCl titrated with 0.0002 M NaOH:
0.0005
0.00045
0.0004
0.00035
0.0003

f1 0.00025
0.0002
0.00015
0.0001
0.00005
0
22

23

24

25

26

27

Vb [mL]

In the vicinity of the equivalence point:

0.0001
0.00009
0.00008
0.00007
0.00006

f1 0.00005
0.00004
0.00003
0.00002
0.00001
0
24.5 24.6 24.7 24.8 24.9

Vb

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25

25.1 25.2 25.3

Tadeusz Grecki

Ionic Equilibria

Weak monoprotic acids and bases

HA H + + A

[ H + ][ A ]
Ka =
[ HA]
B + H 2 O BH + + OH

[ BH + ][OH ]
Kb =
[ B]
K a Kb = K w
pK a + pK b = pK w

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Ionic Equilibria

NH4+: __________
NH3: __________
Dependence of ___ on ___________:

K a0

[ H + ][ A ] +
=
= Ka +
[ HA]
0
0

pK a = pK a0 + log + + log log 0

Using _______________ and setting log 0 = bI (activity coefficient for an
______________________):

I
pK a = 4.757 2 0.51
b' I bI
1 + I

where b' is the ________________ (usually 0.2).

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Tadeusz Grecki

Ionic Equilibria

Best fit: _______________

Temperature dependence of pK 0a :

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Tadeusz Grecki

Ionic Equilibria

Calculating the pH of weak acid

Known: ___________
Unknown: ______________________
[ H + ][ A ]
Ka =
[ HA]
K w = [ H + ][OH ]
Mass balance:

C HA = [ A ] + [ HA]

Charge balance:

[ H + ] = [ A ] + [OH ]

C HA

+
[ H + ][ A ]
[H + ]

[H ] + K a
= [ A ]
= [A ]+
= [ A ]1 +
Ka
Ka
Ka

[ A ] =

C HA K a
[H + ] + K a

From ______________:
C HA [ H + ]
[ HA] =
[H + ] + Ka
From ____:
[OH ] =

Kw
[H + ]

Substituting ____ and _____ into __________________:

[H + ] =

C HA K a
Kw
+
[H + ] + Ka [H + ]

Thus:

[ H + ]3 + [ H + ]2 K a [ H + ](C HA K a + K w ) K a K w = 0
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Tadeusz Grecki

Ionic Equilibria

Simplifying assumption: _____ is negligibly small

[H + ] =

C HA K a
[H + ] + Ka

[ H + ]2 + [ H + ]K a C HA K a = 0
When ____________:
[H + ] =

C HA K a

[H + ]

[ H + ]2 = C HA K a

[ H + ] = C HA K a

Flood's diagram
From ____ and _______________:
C HA

[ H + ] + K a +
K
[ H ] w+
=
Ka
[H ]

Flood's diagram
pH

-2

log C -4

Strong acid

-6

pKa=4.75
pKa=7.53
pKa=10.72

-8
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Tadeusz Grecki

Ionic Equilibria

Degree of dissociation
C HA [ H + ]
[ HA] =
[H + ] + Ka

CHA K a
[A ] =
[ H + ] + Ka

Degree of _____________:
[ A ]
[ A ]
=
=
=
CHA [ HA] + [ A ]
Degree of ____________:
1 =

[ HA]
[ HA]
=
=
CHA [ HA] + [ A ]

Degree of dissociation and formation

1
0.8

degree of formation

degree of dissociation

0.6
0.4
0.2
0
0

8
pH

Page 39

10

12

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Tadeusz Grecki

Ionic Equilibria

Silln's diagram (______________, ____________________)

Acetic acid, 0.01 M, pKa = 4.75

10

12

0
-

[A ]

-2

log C

-4
-6
-8

[HA]

-10
-12

[OH ]

[H ]

-14

pH

1. [H+] is determined from the _______________:

log[ H + ] = pH

2. [OH-] is determined from _________________:

log[OH ] = log

Kw
= pH pK w
[H + ]

3. [A-] is determined from ____________ and ___:

[ A ] =

CHA K a
[ H + ] + Ka

4. [HA] is determined from ____________ and ___:

C HA [ H + ]
[ HA] =
[H + ] + Ka
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Tadeusz Grecki

Ionic Equilibria

pH of a given system can be determined from the _______________:

[ H + ] = [ A ] + [OH ]

Acidic solution, thus _____ can be neglected

[ H + ] = [ A ]

Solution for the proton condition can be easily found on equilibrium diagrams
using the _______________:

log [ H + ] [ A ] [OH ]

Acetic acid, _____ M, pKa = _____

0

10

12

[A-]

-2

log C

-4
-6

Pointer

3.4

-8

[HA]

-10
-12

[OH-]

[H+]

-14

pH

Page 41

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Tadeusz Grecki

Ionic Equilibria

Acetic acid, ____ M, pKa = ____

0

10

12

14

[H+]

-2

[OH-]

-4
-6
-8

[HA]

Pointer

[A ]

6.8

-10
-12
-14

Plotting equilibrium diagrams

1. [H+] and [OH-]: _______ lines at ________ (slopes of __ and __,
respectively)
2. [A-]:
[ A ] =

CHA K a
[ H + ] + Ka

for ____________________
[ A ]

C HA K a
[H + ]

log[ A ] = log C HA pK a + pH
d log[ A ]
=1
dpH
for ___________________ [ A ] C HA
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Tadeusz Grecki

Ionic Equilibria

3. [HA]:
C HA [ H + ]
[ HA] =
[H + ] + Ka

[ HA] = C HA

for ___________________

for ___________________
C HA [ H + ]
[ HA]
Ka
log[HA] = log C HA pH + pK a
d log[HA]
= 1
dpH

4. When __________:
[ A ] = [ HA] =
log[ A ] = log[HA] = log

C HA
2

C HA
= log C HA log 2 = log C HA 0.3
2

What is the pH of 0.001 M NaAc?

____:
[ H + ] + [ HA] = [OH ]

___________, thus _____:

[ HA] = [OH ]

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Tadeusz Grecki

Ionic Equilibria

-2

log Concentration [M]

-4

-6

-8

-10

-12

-14
0

8
pH

Page 44

10

12

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Tadeusz Grecki

Ionic Equilibria

What happens when the acid concentration is __________?

0.001 M HF, pKa = 3.17
[ H + ] = [ F ] + [OH ]

Proton condition:

[H + ] [F ]

10

[H+]

-2

log C

-4
-6

[OH-]

[HF]
[F-]

-8
-10
-12
-14

pH

Page 45

12

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Tadeusz Grecki

Ionic Equilibria

10

[H+]

-2
-4

log C

-6

[OH-]

[HF]
Pointer
[F ] pH=3.26
-

-8
-10
-12
-14

pH

Checking the results:

pH = ____
[OH-] = ______
[HF] = ______
[ H + ][ F ] 10 3.26 10 3.26
=
=
Ka =
3.34
[ HF ]
10
Mass balance:
[ F ] + [ HF ] = 10 3.26 + 10 3.34 =

Algebraic solution:
[ H + ]2 + [ H + ]K a C HA K a = 0
[H + ] =

pH = ____
Page 46

12

14

Tadeusz Grecki

Ionic Equilibria

Low concentrations of very weak acids:

5 x 10-5 M HCN, pKa = 9.32
0

10

12

14

0
+

[H ]

-2

[OH ]
-

[HCN]

-4

[CN ]

log C

-6
-

[CN ]+[OH ]

-8
-10
-12
-14

pH

Mixture of acids
Strong acids represented by ______________.
Strong bases represented by ______________.
Typically ___________ on EquiligrapHs.
Each __________ or _____ represented by the expressions:
CHA K a
[A ] =
[ H + ] + Ka

C BH [ H + ]
[ BH ] =
[H + ] + Ka
+

pH found at the point where _______________.

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Tadeusz Grecki

Ionic Equilibria

0.01 M HAc (Ka = 10-4.75) and 0.001 M HFo (Ka = 10-3.75)

0

10

12

14

0
-2

[Fo ]

[HFo]

-4

log C

[Ac ]

[HAc]

-6
-

[Ac ]+[Fo ]+[OH ]

-8
-10
-12

[OH ]

[H ]

-14

pH

Proton condition: _________________________

Pointer function:
0

10

12

14

0
-

[Ac ]

[HAc]
-2

log C

-4
-6

[Fo ]

[HFo]

Pointer
pH=3.3

-8
-10
-12

[OH ]

[H ]

-14

pH
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Tadeusz Grecki

Ionic Equilibria

Assumptions:
______ negligibly small
__________

[H + ] =

Cf Kf
Ca K a
Kw
+
+
[H + ] + Ka [H + ] + K f [H + ]

[H + ] =

Cf Kf
Ca K a
+
[H + ] [H + ] + K f

+ 2

[ H ] = Ca K a +

Iteration:

[ H ] = Ca K a +

Circular reference:

[ H + ]C f K f
[H + ] + K f
[ H + ]C f K f
[H + ] + K f

Mixture of strong and weak acid:

0.001 M HCl and 0.01 M HAc
[ H + ] = [ Ac ] + [Cl ] + [OH ]

[H + ] =

Ca K a
Kw

[
]
+
Cl
+
[H + ] + Ka
[H + ]

____________________
[ H + ]2 = Ca K a + [ H + ][Cl ]
Solution: pH = _____

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Tadeusz Grecki

Ionic Equilibria

10

12

14

[Ac-]

-2

[Cl-]

-4

log C

-6

[HAc]
[Ac-]+[Cl-]+[OH-]

-8
-10
-12

[OH-]

[H+]

-14

pH

Salt of a weak acid and a weak base

Two independent ________________ linked by the condition that they have the
same ___________________.
[ H + ][ A ] = K a1 [ HA]
[ H + ][ B ] = K a 2 [ BH + ]
[ H + ][OH ] = K w
____ balances:
______ balance:
_______________:

C = [ HA] + [ A ] = [ BH + ] + [ B ]
[ BH + ] + [ H + ] = [ A ] + [OH ]
[ HA] + [ H + ] = [OH ] + [ B ]
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Tadeusz Grecki

Ionic Equilibria

If [H+] and [OH-] _________:

CK a 2
C[ H + ]
=
[ H + ] + K a1 [ H + ] + K a 2
[ H + ]2 = K a 1 K a 2
[ H + ] = K a1 K a 2

pH _______________ on C (provided the assumption above is fulfilled)!

Example: pH of 0.01 M NH4Ac (pKa1 = 4.75, pKa2 = 9.25)

pH = 1 / 2( pK a1 + pK a 2 ) =
The value of __ is coincidental.
Equilibrium diagram:
0

10

12

14

-2

-4

log C

[Ac-]

[NH4+]

-6

-8

[NH3]

[HAc]

-10

-12

[OH-]

[H+]

-14

pH

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Tadeusz Grecki

Ionic Equilibria

Pointer function:
0

10

12

0
-2

log C

-4

[Ac -]

-6

[NH4+]

[HAc]

[NH3]

-8
-10
-12

[OH-]

[H+]

Pointer
pH=7

-14

pH

Full solution:
CK a 2
Kw
C[ H + ]
+
[
]
+
H
=
+
[ H + ] + K a1
[H + ] + Ka2 [H + ]
_______ equation in [H+].

The equation is _____________, thus:

Kw
+
[
]
H

[H + ]
C=

K
1

[ H + ] +
+ 1 + a 2
[
]
[
]
H
K
H
K
+
+

a1
a2

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Tadeusz Grecki

Ionic Equilibria

Example: Dimethylammonium acetate

pKa1 = 4.75 (___________), pKa2 = 10.76 (__________________)

7.8
pH = 7.755

7.7
7.6
7.5
pH 7.4

7.3
7.2
7.1
7
0

-log C

General equation for the titration curve

____ balance:

[ HA] + [ A ] =

____ balance:

[ Na + ] =

CaVa
Va + Vb

CbVb
Va + Vb

[ A ][ H + ]
Ka =
[ HA]
______ balance:

[ H + ] + [ Na + ] = [ A ] + [OH ]
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Tadeusz Grecki

Ionic Equilibria

[ A ] =
[H + ] +
or

[H + ] +

CaVa
K
+ a
Va + Vb [ H ] + K a

CbVb
CV
K
K
= a a + a
+ w+
Va + Vb Va + Vb [ H ] + K a [ H ]

CbVb
CV
K
= HA a a + w+
Va + Vb
Va + Vb [ H ]

K
K
Ca + a
[ H + ] + w+
[H ] + Ka
[H ]
Vb = Va
K

Cb + [ H + ] w+
[H ]

Ca HA [ H + ] + w+
[H ]
Vb = Va
K

Cb + [ H + ] w+
[H ]

Titration of a ___________ with a __________:

Ca [ H + ] + w+
[H ]
Vb = Va
K

Cb + [ H + ] w+
[H ]

Simplifying assumptions: before the equivalence point ____________; after the

equivalence point ________________

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Tadeusz Grecki

Ionic Equilibria

Example: titration of 10 mL 0.1 M HAc with 0.1 M NaOH

14
12
10
pH

8
6
4
2
0
0

6 V 8
b

10

12

14

________________
( pH ) ( pH )

(Vb )
(Vb )
End point determined by the _________ of the ______________. If necessary,
________________ can be obtained in the same manner.
________________:
14
12

pH

10
8
6
4

d(pH)/dVb

2
0
0

6 V 8
b
Page 55

10

12

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Tadeusz Grecki

Ionic Equilibria

____ and ________________:

14
12
10
8
6
4
2
0
-29.90

9.95

10.00

10.05

10.10

-4
-6
-8

Vb

Another way to plot the titration curve: through _____________ :

CbVb
CaVa

Substitution to the general equation:

Ka
(Va + Vb ) K w
+
+

[
H
]

[H + ] + Ka
CaVa [ H + ]

Iteration set ________________ and get the ________________

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Tadeusz Grecki

Ionic Equilibria

14
12

pH

10
8
6
4
2
0
0

1
Fraction titrated

_______________ solution:
[ H + ] [OH ]

CbVb
Ca
=
=
+
[ H ] [OH ]
CaVa
1+
Cb
14
12

pH

10
8
6
4
2
0
0

1
Fraction titrated
Page 57

Tadeusz Grecki

Ionic Equilibria

The plot of _____________________ enables easy comparisons of different

_______________.
Examples:
Different _________ of the acid
14

14

12

12

10

10

pH

pH

4
2
0
0

Va = 10 mL

Va = 20 mL
Va = 30 mL

10

15

20
Vb

25

30

35

40

Different ___ values

14

14

12

12

10

10

8
pH

pH

1
Fraction titrated

Ca = Cb = 0.01 M

Ka = 1e-6
Ka = 1e-5
Ka = 1e-4

Ca = Cb = 0.01 M
Ka = 1e-6
Ka = 1e-5
Ka = 1e-4

1
Fraction titrated

Page 58

10
Vb

15

20

Tadeusz Grecki

Different __________________________:
14

14

12

12

10

10

pH

pH

Ionic Equilibria

pKa = 4.75
Cb = 0.01 M
Ca = 0.0001 M

6
4

Ca = 0.001 M

2
0
1

pKa = 4.75
Cb = 0.01 M

Ca = 0.0001 M
Ca = 0.001 M

Ca = 0.01M
0

Ca = 0.01 M

Fraction titrated

15

Different concentrations of the _____:

14

14

12

12

10

10

pKa = 4.75
Ca = 0.01 M

Cb = 0.0001 M

pH

pH

10
Vb

Cb = 0.001 M

Cb = 0.0001 M
Cb = 0.001 M
Cb = 0.01 M

0
1

pKa = 4.75
Ca = 0.01 M

Cb = 0.01 M
0

Fraction titrated

Page 59

0
0

500

1000
Vb

1500

2000

Tadeusz Grecki

Ionic Equilibria

Titration of a ___________ with a _________:

[ H + ] + BH

CbVb
CV
K
= A a a + w+
Va + Vb
Va + Vb [ H ]

CV
= b b =
CaVa

where

BH

BH

[ H + ] [OH ]

Ca
[ H + ] [OH ]
+
Cb

[ BH + ]
[H + ]
=
= +
;
CB
[ H ] + K BH
+

K HA
[ A ]
=
=
C HA [ H + ] + K HA

14

14

10

pKa = 4.75
pKb = 5
Ca = 0.01 M
Va = 10 mL

12

pKa = 4.75
pKb = 5
Ca = 0.01 M

12

10
8

pH

pH

6
4

Strong base
Kb = 5

Strong base

Kb = 5
0

0
0

1
Fraction titrated

Page 60

10
Vb

15

20

Tadeusz Grecki

Ionic Equilibria

Titration error
At the equivalence point ________

CbVb ' = CaVa

where Vb is Vb at the _______________

Vb ' =

CaVa
Cb

Titration error:
T .e. =

Vep Vb '
Vb '

Vep
Vb '

1 =

Vep
CbVep
1 =
1 = ep 1
CaVa
CaVa
Cb

At the equivalence point and its vicinity:

Va + Vb Cb + Ca
=
Va
Cb
Also, near the equivalence point, ____________ , thus _____________

Ka
[H + ]
[H + ]
1 = +
1 = +

[H ] + Ka
[H ] + Ka
Ka
ep 1 = 1 +

(Va + Vb ) K w

+ [ H + ]
CaVa [ H ]

(Va + Vb ) K w
[H + ]
+
ep 1 =
[ H ]

CaVa [ H + ]
Ka
[ H + ]ep
(Ca + Cb ) K w
+
ep 1 =
[ H ]ep
+

CaCb [ H ]ep
Ka

Page 61

Tadeusz Grecki

Ionic Equilibria

Example: 0.1 M HAc, 0.1 M NaOH, pHep = __ instead of pH = _____ at the

equivalence point

10 8
ep 1 = ( 20)(10 10 ) 4.75 =
10
6

Titration of a weak base with a strong acid:

ep 1 =

(Ca + Cb ) +
K w
Ka

[
H
]
ep
CaCb
[ H + ]ep [ H + ]ep

Page 62