Titrasi Polifungsional

Asam dan basa

materi ketiga
1. Cara menangani sistem kompleks asam-
basa
Sistem kompleks didefn sebagai larutan yg dibuat
dari :
(1) Suatu asam or basa yg mpy 2 or lebih proton
asam atau gugus fungsi
H3PO4
Ca(OH)2
(2) Dua asam or basa dgn kekuatan yg bbeda
HCl + CH3COOH
NaOH + CH3COO-
3) Suatu substansi amfiprotik dapat btindak
sbg asam dan basa sekaligus

HCO3- + H2O <=> CO32- + H3O+

HCO3- + H2O <=> H2CO3 + OH-
NH3+CH2COO- + H2O <=> NH2CH2COO- + H3O+
NH3+CH2COO- + H2O <=> NH3+CH2COOH + OH-
H PO H 2 PO4
K a1

Ka 2 2
HPO4
Ka 3
PO4
3
3 4
Kb3 Kb2 Kb1

Ka1Kb3=Kw Ka2Kb2=Kw Ka3Kb1=Kw

Ka1=110-2 >Ka2=110-7> Ka3=110-12

Ktotal=Ka1Ka2 Ka3=110-21
 pH dr H3PO4

1. Hitung pH dari larutan 0.100M H3PO4 .

K a1
1000 K a 2 .is.negligible
Ka2

[ H ].[ H 2 PO4 ]
K a1 1 10 2
0.100 H

H+ tdk dapat diabaikan

 pH dr HA -

larutan pH dr HA-
Ka2
HA- A2- + H+ CHA K a 2 K w
[H ]
CHA
1
Kb2
HA- H2A + OH-
Ka1 K a1
 pH of HA -

Hitung pH dari larutan 0.100M NaHCO3

CHA K a 2 K w
[H ]
Ka1=110-6 >Ka2=110-10 C
1 HA
K a1

Ka2CHA- =110-10 1.00>>Kw.Kw is negligible

C HA 1.00
1 10 6

K a1 1 10 6
pK a1 pK a 2
1....isnegligible...... pH 8
2
 pH of HA -

Hitung pH larutan dr 0.0100M NaH2PO4.

CHA K a 2 K w
[H ]
CHA
1
K a1
Ka1=110-2 >Ka2=110-7> K a3=110-12

Ka2CHA- =110-7 0.01>>Kw.Kw is negligible

C HA 0.01
2
1 CHA K a 2
K a1 1 10
[H ]
CHA
1....is.not.negligible 1
K a1
 pH of HA -
Hitung pH dr larut 1.0010-3M Na2HPO4

Ka2=110-7> Ka3=110-12
Ka1=110-2 >
CHA K a 2 K w
[H ]
CHA
1
K a1
Ka2CHA- =110-10 0.001=110-13 Kw isnot negligible

C HA 0.001
1 10 4
1....is.negligible
K a1 1 10 7
CHA K a 2 K w
[H ]
CHA
K a1
 Problems

1. Memaknai : Ka1>Ka2>Ka3
2. Hubungan antr Ka and Kb dlam suatu
asam/basa konjugat
 Example 13-1, 2, 3
1. Calculate the hydronium ion concentration of
0.100M NaHCO3 solution.
2. Calculate the hydronium ion concentration of
1.0010-3M Na2HPO4 solution.
3. Find the hydronium ion concentration of
0.0100M NaH2PO4 solution.
Mixtures of Strong and Weak Acids

Mixtures of Strong and Weak bases?

Problem(P325, 13-25): Identify by letter the curve you would expect in
the titration of a solution containing
(a) disodium maleate, Na2M, with standard acid (1.3x10-2, 5.9x10-7)
(b) pyruvic acid, HP, with standard base (3.2x10-3)
(c) sodium carbonate, Na2CO3, with standard acid (1.5x10-4, 4.69x10-11)
 Campuran asam lemah dan kuat
As sulfat mrpk satu contoh dr asam kuat dan sekaligus asam lemah dlam sutu larutan (Ka2 = 1.02 X 10-2). Marilah
kita menghitung konsentrasi ion H dari 0.0400M
H2SO4 H+ +HSO4- SO42- + H+
We will first assume that the dissociation of HSO 4 is negligible because of the large excess of H30+ resulting from
the complete dissociation of H2SO4. Therefore,
2
0.04 [ SO4 ]
[H+] [HSO4 ] 0.0400 M Ka
0.04
This result shows that [SO4- ] is not small relative to [HSO4 ], and a more rigorous solution is required.
From stoichiometric considerations, it is necessary that

[H+] = 0.0400 + [SO42-] [SO4] = [H+] - 0.0400 CH SO , = 0.0400 = [HS04- ] + [SO42-]

2 4

[HSO4-] = 0.0800 - [H3O+]

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 Campuran dari asam kuat dan lemah
Sulfuric acid is unusual in that one of its protons behaves as a strong acid in water and
the other as a weak acid (Ka2 = 1.02 X 10-2). Let us consider how the hydronium ion
concentration of sulfuric acid solutions is computed using a 0.0400M solution as an
example.
H2SO4 H+ +HSO4- SO42- + H+
We will first assume that the dissociation of HSO4 is negligible because of the large
excess of H30+ resulting from the complete dissociation of H2SO4. Therefore,

[H+] = 0.0400 + [SO42-] [HSO4-] = 0.0400 - [SO42-]

2 2 2
[ H ] [ SO4 ] (0.04 [ SO4 ]) [ SO4 ]
Ka
2
[ HSO4 ] (0.04 [ SO4 ])
Curves for the titration of strong acid / weak acid mixture with 0.1000 M
NaOH. Each titration is on 25.00 ml of a solution that is 0.1200 M in HCl
and 0.0800 M in HA.
Curves for the titration of 25.00 ml of polyprotic acid with 0.1000M NaOH solution .
A)0.1000 M H3PO4, Ka1=110-2 >Ka2=110-7> Ka3=110-12
B) 0.1000M oxalic acid, Ka1 =5.6 10-2 and Ka2 = 5.4 x 10-5
C) 0.1000 M H2SO4 Ka2 = 1.02 10-2
Titration curves for
polyfunctional acids

Titration of 20.00 ml of 0.1000 M H2A with 0.1000 M NaOH.

For H2A, Ka1= 1.00 103 and Ka2 = 1.00 107 .
Titration of 25.00 ml of 0.1000M maleic acid with 0.1000M NaOH.
HOOC-C=C-COOH
pKa1=1.89 ,pKa2=6.23
E-HOOC-C=C-COOH Z-HOOC-C=C-COOH
Fractional composition diagram for Fractional composition diagram for
fumaric acid (trans-butenedioic acid). maleic acid (Cis-butenedioic acid).
pKa1=3.05 ,pKa2=4.49 pKa1=1.89 ,pKa2=6.23

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 amino acids

alanine

The amine group behaves as a base, while the carboxyl group acts as an acid.

Aspartic acid
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 1-Determining the pK values for amino acids
Amino acids contain both an acidic and a basic group.

NH2-CH2-COOH +NH3-CH2-COO- Zwitterion

formation
NH3-CH2-COO- + H2O NH2-CH2-COO- + H3O+
+

[NH2 - CH2 - COO - ] [ H3O ]

Ka
[ NH3 - CH2 - COO - ]

+
NH3-CH2-COO- + H2O +NH3-CH2-COOH + OH-
[ NH 3 - CH 2 - COOH] [ OH ]
Kb
[ NH 3 - CH 2 - COO - ]

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2-Determining the pK values for amino acids
Amino acids contain both an acidic and a basic group.

NH2-CH2-COOH +NH3-CH2-COO- Zwitterion formation

Kb Ka
+
NH3-CH2-COOH +NH3-CH2-COO- NH2-CH2-COO-

Ka1=510 -3 Ka2=210-10

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 B A

Curves for the titration of 20.00ml of 0.1000M alanine with

A) 0.1000 M NaOH
B) 0.1000M HCl.
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Iso electric point:
The pH at which the average charge of the polyprotic acid is zero

The zwitterion of an amino acid, containing as it does a positive and a negative

charge, has no tendency to migrate in an electric field,

+
NH3-CH2-COO-
whereas the singly charged anionic and cationic species are attracted to
electrodes of opposite charge.
NH2-CH2-COO- + NH3-CH2-COOH

No net migration of the amino acid occurs in an electric field when the pH of
the solvent is such that [anionic] = [cationic], which is pH dependent.

The pH at which no net migration occurs is called the isoelectric point; this
point is an important physical constant for characterizing amino acids. The
isoelectric point is readily related to the ionization constants for the species.
Thus, for glycine,

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 1-Determining iso electric point for amino acids
+
NH3-CH2-COO- Zwitterion formation

[NH 2 - CH 2 - COO - ] [ H 3O ] [ NH 3 - CH 2 - COOH ] [ OH ]

Ka Kb
[ NH 3 - CH 2 - COO - ] [ NH 3 - CH 2 - COO - ]

In iso electric point [NH 2 - CH 2 - COO - ] [ NH 3 - CH 2 - COOH ]

K [ H O ] Kw
K a [ H 3O ] K [OH
] [ H 3O ] a 3
[ H 3O ] a
Kb
K b [OH ] Kb

Ka Kw
2K Kw
[ H 3O ] a [ H 3O ]
Kb Kb

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2-Determining iso electric point for amino acids

pKa1=2.35 Ka2=9.87
NH3-CH2-COOH +NH3-CH2-COO- NH2-CH2-
+

COO-

pK a1 pK a 2
pH
2

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 Method1=method2
Kb Ka
OH H 2 A HA A H

Kw
H 3O Ka
Kb
Kb2 K b1
H 2 A K HA K A
a1 a2
pKa1 pKa 2
H 3O Ka1 Ka 2
2
Kw Kw
Ka=Ka2,,,,,,,,,,,,Kb=Kb2 K a1
K b K b2
Kw
H 3O Ka Ka1 Ka 2
Kb
 Formol titration
For simple amino acids, Ka and Kb are generally so small that their
quantitative determination by neutralization titrations is impossible.
+
NH3-CH2-COO- + OH-
Product
+
NH3-CH2-COO- + HCOH CH2=NCH2COOH
Amino acids that contain more than one carboxyl or amine group can
sometimes be determined.
If the Ka values are different enough (104 or more), stepwise end points can
be obtained just like other polyfunctional acids or bases as long as the Ka
values

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