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QCA10e-ch10(4)

Chapter 10 discusses polyprotic acid-base equilibria, focusing on diprotic acids and buffers, and the behavior of amino acids as zwitterions. It explains the concepts of principal species, fractional composition equations, and the isoionic and isoelectric points in relation to polyprotic acids. The chapter also highlights the biological functions of proteins and their structural dependence on amino acid sequences.

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2 views27 pages

QCA10e-ch10(4)

Chapter 10 discusses polyprotic acid-base equilibria, focusing on diprotic acids and buffers, and the behavior of amino acids as zwitterions. It explains the concepts of principal species, fractional composition equations, and the isoionic and isoelectric points in relation to polyprotic acids. The chapter also highlights the biological functions of proteins and their structural dependence on amino acid sequences.

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Chapter 10

Polyprotic Acid-Base Equilibria


10-1 Diprotic Acids and Bases

10-2 Diprotic Buffers

10-3 Polyprotic Acids and Bases

10-4 Which Is the Principal Species?

10-5 Fractional Composition Equations

10-6 Isoelectric and Isoionic pH


Carbon Dioxide in the Air
Carbon dioxide is being injected into the atmosphere in sufficient quantity to alter the
cycle of CO2.

• Upper curve: atmospheric CO2 deduced from air


trapped in Antarctic ice and direct atmospheric
measurements
• Lower curve: atmospheric temperature at the level
where precipitation forms as deduced from isotopic
composition of ice
• Rise in global temperature: combined average
annual temperature for land and ocean minus mean
temperature
10-1 Diprotic Acids and Bases

The amino acid building blocks of proteins have the general structure

A zwitterion is a molecule with both positive


and negative charges.
Table 10-1
The Acidic Form, H2L+

It appears that the H2L+ will dissociate only partly, and the resulting HL will hardly
dissociate at all. For this reason, we make the (superb) approximation that a
solution of H2L+ behaves as a monoprotic acid, with Ka = K1
The Basic Form, L-
The Intermediate Form, HL
HL is both an acid and a base.

(양쪽성 양성자성)
A molecule that can both donate and accept a proton is said to be amphiprotic.
the charge balance is

(10-10)
(10-11)
Simplified Calculation for the Intermediate Form

(10-12)
Summary of diprotic acid calculations

• A diprotic acid H2A exists as H2A, HA- and A2- in


solution and thus acid may be prepared with any
of the above substance.

• Case 1: Solution of H2A.


• Case 2: Solution of HA-.

• Case 3: Solution of A2-.


10-2 Diprotic Buffers
A buffer made from a diprotic (or polyprotic) acid is treated in the same way
as a buffer made from a monoprotic acid. For the acid H2A. we can write two
Henderson-Hasselbalch equations, both of which are always true. If we
happen to know [H2A] and [HA-], then we will use the pK1 equation. If we
know [HA-] and [A2-], we will use the pK2 equation.
_

.10

.10
Good example!!!

1.250

2.76

46.93

0.02166

0.02166 0.02166
46.93
73.98
10-3 Polyprotic Acids and Bases
10-4 Which Is The Principal Species?
Figure 10-3 summarizes how we think of a triprotic system. We determine the
principal species by comparing the pH of the solution with the pKa values.
10-5 Fractional Composition Equations
Monoprotic Systems
Diprotic Systems
등전 등이온
10-6 Isoelectric and Isoionic pH
H2A+ HA

A-
HA
(등이온점)
The isoionic point (or isoionic pH) is the pH obtained when the pure, neutral polyprotic acid HA (the
neutral zwitterion) is dissolved in water. The only ions are H2A+, A-, H+, and OH-. Most alanine is in the
form HA, and the concentrations of H2A+ and A- are not equal to each other.
The isoelectric point (or isoelectric pH) is the pH at which the average charge of the polyprotic acid is 0.
Most of the molecules are in the uncharged form HA, and the concentrations of H2A+ and A- are equal to
each other. There is always some H2A+ and some A- in equilibrium with HA.
(등전점)

When alanine is dissolved in water, the pH of the solution, by definition, is the isoionic
pH. Because alanine (HA) is the intermediate form of the diprotic acid, H2A+ , [H+] is
given by

Isoionic point:
The isoelectric point is the pH at which [H2A+] = [A-], and, therefore, the average
charge of alanine is 0. To go from the isoionic solution (pure HA in water) to the
isoelectric solution, we could add just enough strong acid to decrease [A -] and
increase [H2A+] until they are equal. Adding acid necessarily lowers the pH. For
alanine, the isoelectric pH must be lower than the isoionic pH.
We calculate the isoelectric pH by first writing expressions for [H2A+] and [A -]:

Isoelectric point:
Proteins Are Polyprotic Acids and Bases

Proteins perform biological functions:


• Catalysis of chemical reactions
• Immune response to foreign substances
• Transport of molecules across membranes
• Control of genetic expressions
• Structural support

“3D structure and function of a protein is determined by the sequence of amino acids.”
Surface acidity of a solid (고체의 표면 산도)” and “pH of zero charge (영전하) (pzc)

• Mineral, clay, and even organic surfaces behave as acids and bases.
• The silica (SiO2) surface of sand or glass can be thought of as a diprotic acid.

• The pH of zero charge is the pH at which {SiOH2+} = {SiO- } and, therefore, the
surface has no net charge.
• The pH of zero charge is
• Colloidal particles remain dispersed when charged, but they flocculate near
the pH of zero charge.
Homework :

9th: 10-4, 10-5, 10-12, 10-21,10-23, and 10-29

10th: 10-4, 10-5, 10-12, 10-21,10-23, and 10-29

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