Agua:

Un enfoque bioqumico de su
importancia
Profra. Ana Edith Ayala Rodrguez



EL AGUA Y SOLUCIONES ACUOSAS
I . Propiedades del agua
II. cidos, Bases y Buffers
III. Problemas y aplicaciones
I. Propiedades del agua
A. Estructura e interacciones
1. Geometra
2. Enlaces Hidrgeno
3. Propiedades Fsicas
4. Conductividad, autoionizacin y otras
propiedades qumicas.
B. El agua como solvente
1. Polaridad
2. Propiedades anfipticas
3. Movilidad de protones (iones Hidronio e
Hidroxilo)
II. Acidos, bases y buffers
A. Reacciones cido-base
1. Definiciones
2. Fuerza de un cido: constante de disociacin
3. El pH: concentraciones relativas de cidos y bases
B. Buffers
1. Qu es un buffer ?
2. Como escoger y preparar un buffer
Water
A water molecule (H
2
O), is
made up of three atoms ---
one oxygen and two hydrogen.

H
H
O
Water is Polar
In each water molecule, the oxygen
atom attracts more than its "fair
share" of electrons
The oxygen end acts negative
The hydrogen end acts positive
Causes the water to be POLAR
However, Water is neutral (equal
number of e- and p+) --- Zero Net
Charge

Structure of a Water Molecule











What keeps a water molecule
together? Polar Covalent bond

What is a polar bond?
Unequal sharing of electrons.

What is a Covalent Bond?
A bond in which electrons are shared.

The bonds within one molecule are
called intramolecular bonds.

H20
Molecular Structure of Water
One oxygen atom
Two hydrogen atoms
H
2
O
Not symmetrical
Electrons spend more time near the oxygen and
less near the hydrogen
Water molecule is polar
O
H H
+ +
-
Estructura de la molcula de agua
El permetro representa la
envoltura de Van der Waals
de la molcula (los
componentes que se
atraen estn balanceados
con los que se repelen). El
modelo esquemtico de la
molcula indica los enlaces
covalentes.
(Tomado de Bioqumica de
Voet)
DIRECCIN DEL MOMENTO
DIPOLAR
o
+

o
+
2o
-

Radio de Van der Waals del
atomo de H = 0.12nm
Radio de Van der Waals del atomo
de O = 0.14nm
Longitud del enlace
covalente
Polarity and Water Molecule
Water is Polar.

Polar substances charge is neutral, but one end of the molecule is
positive and the other end is negative.

Non-polar substances, like fats, will NOT dissolve in water. These
substances are neutral and there is no excess charge at one end of
the molecule.

A basic rule is: Like dissolves in Like.
This means that, in general, polar substances will dissolve in other
polar substances, and that non-polar substances will dissolve in
other non-polar substances. Polar substances will not dissolve
non-polar substances.
http://www.mrowen.com/chem11/solutions/solutions40.pdf


Why does Oxygen attract electrons more than
hydrogen?
Electronegativity- is a measure
of the ability of an atom in a
chemical compound to attract
electrons.
Electro negativity depends on 2 factors
1. The number of protons in the nucleus.
2. The distance the electrons are from the nucleus.
O
H
H
104.5
o
C
O
H H
2o

o
+
o
+
- The water molecule is bent.
- O (3.5) is more electronegative than H (2.2).
H
2
O is highly polar with a net dipole.
has 33% ionic character.
(2) Characteristics of Water
1 (Angstrom)
= 10
8
cm
= 0.1 nm
- H
2
O interacts through hydrogen bonds.

b.p. (
o
C) m.p.
Water 100 0
MeOH 65 98

The name is bond---H bond


HYDROGEN BONDS
What is a hydrogen bond?
A chemical bond in which a
hydrogen atom of one molecule is
attracted to an electronegative
atom, generally a nitrogen, oxygen,
or flourine atom.

The hydrogen of one water
molecule bonds with the oxygen of
another water molecule and so on.
This is an example of
intermolecular bonding.

Each water molecule can form a
maximum of 4 hydrogen bonds.

They form, break, and reform with
great frequency
Hydrogen bonds
What are they?
A special case of permanent dipole-dipole interactions
They are stronger than van der Waals forces.
Molecules with hydrogen bonds have higher boiling points than molecules that
dont.
Hydrogen bonds
What do you need?
A hydrogen atom covalently bonded to an electronegative atom N, O
or F.
If only one of these conditions is met, you dont get hydrogen bonding.
A lone pair of electrons on the electronegative atom.
Hydrogen bonds
Give me an example!
This does not have any hydrogen bonds. Carbon is not very electronegative, and it
has no lone pairs of electrons in methane.
methane, CH
4

Hydrogen bonds
Give me a real example!
This does have hydrogen bonds.
Nitrogen is very electronegative, and it has one lone pair of electrons in ammonia.
ammonia, NH
3

Hydrogen bonds
Give me another example!
This has not one, but two hydrogen bonds.
Oxygen is very electronegative, and it has two lone pairs of electrons in water.
water, H
2
O
Hydrogen bonds
Remember, you need:
A hydrogen atom covalently bonded to an electronegative atom N, O
or F.
If only one of these conditions is met, you dont get hydrogen bonding.
A lone pair of electrons on the electronegative atom.
Early evidence of hydrogen bonding
Many elements form hydrides
Plot BP of hydrides of Group 4 elements
BP increases as we go down a gp
Van der Waals forces



Plot BP of hydrides of gp 5,6, and 7
Similar results
EXCEPT the hydride of the first element
in each of groups 5,6, and 7
NH
3
, H
2
O, and HF must be having some
additional intermolecular forces of attraction


Hydrogen attached directly to most electronegative atoms
Partial positive charge of hydrogen
Partial negative charge on the electronegative atoms
as well as at least one lone pair







The partially positive hydrogen strongly
attracted to the lone pair
Interaction much stronger than
dipole-dipole interaction

Ethanol (BP = 78.5 C)
Methoxymethane (BP = -24.8 C)
100-fold elevation of BP

Hydrogen bonding in water
H-bond partly electrostatic (90%), partly covalent (10%)
Approximated by the following bonds:
+
a
(A-H B); +
b
(A
-
H
+
---B: ionic); +
c

(A
-
H----B
+
: covalent); +
d

(A
+
H----B:
ionic); +
e
(H
-
A---B
+
: covalent)
+ = +
a
++
b
++
c
++
d
++
e

X-Ray spectroscopic evidence suggests that these interactions shift
within a femtosecond
Nuclear quantum effects strengthen the H-bond by increasing the dipole moment
Donor hydrogen stretches away from its oxygen
Acceptor lone-pair stretches away from it oxygen
Both oxygens being pulled towards each other


Cute Movie:
http://www.northland.cc.mn.us/biology/Biology1111/animations/hydrogenbonds.html


Hydrogen bond: A type of dipole force.
An electrostatic attractive force between molecules. Found when a H
atom is bonded to N, O or F.
Weaker than covalent bonds (23 kJ/mol in water).
CC: 350 kJ/mol, OH: 470 kJ/mol.

Can a H atom bonded to C form a H-bond?

The answer is No (for the moment).
C (2.5) is only slightly more electronegative than H.

Hydrogen Bonding
+ attracted to
Each H
2
O is bonded
to its nearest
neighbor
Physical States
Vapor
- Hydrogen bonding in ice.

Each H
2
O forms 4 H-bonds.

In liquid water,
each H
2
O forms, on average,
3.4 H-bonds.

This is why less dense ice
floats in liquid water, and why
water expands when frozen.
- Directionality of the H-bond:
The bond strength depends not only on the distance between
the H or X (N or O), but also the angle of the atoms in space.
Thus, Hydrogen bonds can vary in strength from
very weak (1-2 kJ mol
1
) to strong (20~30 kJ mol
1
).
- Common H-bonds in biological systems:
- Good solvent for polar and ionic material such as salts, small polar molecules
(amino acids, sugars, nucleic acids ) and the exterior of proteins.

- Solubility enhanced for molecules that can form H-bonds i.e. hydroxy, keto,
carboxy, amino groups, and these are termed hydrophilic (water loving) groups.

- Solubility reduced for molecules that cannot form H-bonds (i.e. hydrocarbons
such as alkanes, alkenes), and these are termed hydrophobic (water fearing)
compounds.
Polar
Nonpolar
Amphipathic
phospholipids
(3) Aqueous (Water-based) Solutions
Water is a polar solvent.
- Solvation of crystalline salt: Water breaks up the salt crystal
lattice by H-bonding with the individual ions. hydration
High dielectric constant (c) of water makes
ionic interactions weaker. (F= Q
1
Q
2
/c r
2
)
- Entropy-driven: AG < 0 : AH 0, AS 0 (of ions)

- Nonpolar gases (O
2
, CO
2
) and nonpolar compounds
(benzene, hexane) are not soluble in water.

AH > 0 breaking up the water H-bonds.
AS < 0 cage-like, highly ordered H
2
O molecules
around the hydrophobic compounds.

Overall, AG > 0.
This is why we need a water soluble O
2
carrier, hemoglobin.
- Amphipathic (Amphiphilic) compounds contain
both polar (hydrophilic) & non-polar (hydrophobic) regions
(ex. fatty acids)
In aqueous solution: water hydrates the hydrophilic portion
but excludes the hydrophobic region to give micelles and
lipid bilayers in a process that reduces entropy (+S)
or increases the order of the lipid molecules, but increases the
entropy of surrounding water (basis of cell membranes)

Formation of micelles

Not favorable
AG > 0


Favorable
AG < 0

Hydrophobic Interactions
(4) Hydrophobic Interactions

The tendency of hydrophobic (lipophilic) groups to form
intermolecular aggregates in an aqueous medium,
and analogous intramolecular interactions.

The name may be misleading, not repulsion between
water and hydrophobic compounds, per se,
but effects of the hydrophobic groups on the water-water
interactions are the driving force for the hydrophobic interactions.

Hydrophobic interaction is driven by AS 0.

Clathrate structure
(Ordered water structure surrounding a compound.)



First hydration shell of MeOH/H
2
O solution.





Neither the negative end nor the positive end of the dipole
wants to be pointed to the non-polar molecule, hence,
the water molecules in the hydration shell tend to be oriented
with their dipole moments oriented tangentially to the non-polar,
neutral molecule, resulting in a cage-like, or 'clathrate' structure
around the non-polar group.
H
2
O
O
O
O
O
O
O
O
O
O
Hexane
O
OO
O
O
O
O
O
O
H
2
O
O
O
O
O
Hexane
O
O
O
AG > 0
AS < 0
AG < 0
AS > 0
Spontaneous
O
O
O
O
O
O
O
The transfer of nonpolar solutes from non-aq. solvent to water.
Note that water molecules surrounding the non-polar solutes are
highly ordered (red).
Hydrophobic Interactions
H
2
O
O
O
O
O
O
O
Less ordered bulky water solvent
Supose there are 11 water molecules,
all disordered.
O
O
O
O
O
O
Add oil drops
O
O
O
O
O
Highly ordered water molecules
(9 molecules) surround oil drops.
The rests (2 molecules) are
still disodered
When the oil drops come closer,
they will spontaneouly collapse onto
themselves to become a larger drop.
We know this from experience.
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
Now, 3 previously orderd water molecules
become disordered, increasing "disorder"
in the system (AS > 0), and leading to
a state of lower G (AG < 0).
Step 1
Step 2
Step 3
Hydrophobic interactions are Important in protein folding,
biomembrane organization, and enzyme-substrate binding.

Hydrophobic Interaction and Protein Folding:
Hydrophobic interactions are the most important noncovalent
force that will cause the linear polypeptide to fold into
a compact structure.
However, it is not the interactions between side chains of
hydrophobic amino acids per se (mainly van der Waals)
that induce the strong interaction, but the increase in entropy
gained by the removal of hydrophobic surface area
from ordered solvating water.
The aggregation of the hydrophobic surfaces gives
the tightly packed core of a protein.
Phe
Leu
O
O
O
O
O
O
O
O
folding
AS > 0
Phe
Leu
O
O
O
(5) van der Waals Interactions

Dispersion forces (London forces):
Intermolecular, attractive force arising from temporary dipoles.

b.p. of noble gases:
He 269C
Ne 246C
Ar 186C

Original temporary
dipole
Induced
dipole
(5) van der Waals Interactions

Dipole-dipole interactions:
Intermolecular, attractive force arising from permanent dipoles.
ethane
fluoroethane
b.p. 184.5 K
b.p. 194.7 K
Permanent dipole
o+ o
All molecules experience dispersion forces.
Dipole-dipole interactions are not an alternative to
dispersion forces. - They occur in addition to them.
(6) Noncovalent
interactions are:

-individually weak, but their
cumulative effects are critical
in biological functions.
(7) Water can be part of a proteins structure
Tightly bound water molecules (red spheres) in hemoglobin.
Water can play an important role in protein function.
Water chain
in cytochrome f.
Protons move across
the membrane,
probably through
proton hopping.
(8) Solutes Affect the Colligative Properties of Aqueous Solutions:
[H
2
O]
eff
is lower in solution than in pure water.
Colligative: depending on the
number of particles (as molecules)
and not on the nature of the
particles
<pressure is a colligative property>
Other colligative properties
of solution:
b.p. l
m.p.
T = K
f
m
Kb = 0.512 C kg/mol
K
f
= 1.86 K kg/mol
T
b
= K
b
m
Osmotic pressure
(8) Solutes Affect the Colligative Properties of Aqueous Solutions:
[H
2
O]
eff
is lower in solution than in pure water.
- Osmosis: water moves from a region of high to low water conc.
- Effect can be measured by the vant Hoff equation:
H = E (i
n
c
n
)RT
H - Osmotic pressure,
force required to resist water movement

i - vant Hoff factor
- measure of extent to which the solute
dissociates into two or more ionic
species (a fraction, no units)
2 is the maximal possible value for NaCl
1 is non-ionizing

c - molar concentration of solute (M)
R - gas constant (0.08206 Latm/K mol)
T absolute temperature (K)

Osmolarity: The osmotic concentration of a solution expressed as
osmoles of solute per liter of solution.
Osmolarity is dependent on the
number of particles in solution
but independent of the nature
of the particles.
Osmolarity of a simple solution
= (molarity) X
(the number of particles per molecule)
1 mM NaCl
Total osmolarity = 2 mOsM
The number of osmotically active
particles in solution
1 M glucose solution = 1 OsM
1 M NaCl = 2 OsM
1 M Na
2
SO
4
= 3 OsM
isotonic
hypertonic
hypotonic
Water moves fairly freely across
the cell membrane.

Not all molecules can cross the
membrane
(semi-permeable).
Q: Why do the cells store energy as polysaccharides, not
as individual glucose molecules?
Examples of Osmosis

1. Fresh water fish in salt water
2. A cell in distilled water
3. Blood
4. Bacteria & salt
5. Wilted lettuce
[2] Ionization of Water, Weak Acids, and Weak Bases

(1) Ionization of Water:

Slight tendency of H
2
O to undergo reversible ionization to hydrogen ion (proton) and
hydroxide ion:

H
2
O H
+
+ OH

BUT, free protons do not exist in solution:
protons are hydrated to hydronium ions:

H
2
O + H
+
H
3
O
+
(very fast due to proton hopping)
The ionization is expressed by an equilibrium constant (K
eq
)
H
2
O H
+
+ OH

[H
+
][OH

]
Keq =
[H
2
O]

At 25 C, [H
2
O] = 55.5 M.

(55.5 M)(Keq) = [H
+
][OH

] = Kw (ion product of water)

Keq is 1.8 x 10
-16
M as determined by electro-conductivity exp.
Kw = (55.5 M)(1.8 x 10
16
M) = [H
+
][OH

] = 1.0 x 10
14
M
2

At neutral pH, [H
+
] =[OH

] and [H
+
][OH
-
] = [H
+
]
2

[H
+
] = 1.0 x 10
7
M in pure water at 25C.
Since Kw is constant,
when [H
+
] > 10
-7
M [OH

] < 10
-7
M, and
when [H
+
] < 10
-7
M [OH

] > 10
-7
M.

(2) The pH Scale
1
pH = log
[H
+
]

= log [H
+
]

pH 7 is neutral,
[ H
+
] = [OH

]
pH < 7 is acidic,
[ H
+
] > [OH

]
pH > 7 is basic,
[OH

] > [ H
+
]

pH + pOH = 14
The pH must be controlled in
an organism; where the breakdown
in pH regulation can lead to serious
metabolic disturbances:
The pH of blood is normally kept within
7.35~7.45.
Outside the narrow range, the organism can not
function.
The pH of the cytosol of most cells is ~ 7.4,
however, in the lysosomal organelles the pH is ~
5.0. This is the pH at which the degradative
enzymes (proteases) of the lysosome function
best, and they are actually inactive at cytosolic
pH!

Negative pH ?
YES

http://en.wikipedia.org/wiki/PH

Most substances have a pH in the range 0 to 14, although extremely
acidic or extremely basic substances may have pH less than 0 or greater
than 14.

An example is acid mine runoff, with a pH = 3.6.
What is the pH of 0.1 M NaOH solution ? (p.62)

NaOH is a strong base and completely ionized in dilute aq. solution.
[OH

] = 0.1 M.
From K
w
= [H
+
][OH

] = 1.0 10
14
M
2
,
[H
+
] = 10
-14
M
2
/0.1 M = 10
13
M. pH = log10
13
= 13.
Or, from [OH

] = 0.1 M, pOH = log 10

1
= 1.
Since pH + pOH = 14, pH of the solution is 13.

What is [OH

] in a solution with [H
+
] of 1.3 x 10
4
M?

[H
+
] = K
w
/[OH

] = 10
14
M
2
/1.3 10
-4
M
= 0.769.... 10
10
M
= 7.7 10
11
M
(Notice the number of significant figures.)
pH meter: History and How it works
http://center.acs.org/landmarks/landmarks/phmeter/phmeter.html
(3) Weak Acids and Weak Bases
Conjugate base of a strong acid is a weak base.

- Acids proton (H
+
) donors; Bases proton acceptors
HA H
+
+ A

(A

: conjugate base)

[H
+
] [A

]
- K
eq
= K
a
(dissociation constant) =
[HA]

- Stronger acids larger K
a
lower pK
a
( logK
a
)

phosphoric acid (H
3
PO
4
): pK
a
= 2.34;
monohydrogen phosphate (HPO
4
2
): pK
a
= 12.4

(4) pK
a
and Titration Curve
- How do pH values of an acetic acid
solution
vary with added [OH

]?
a titration curve

- Constructed by:
a) experiment
b) H-H equation

midpoint pH of titration = pKa of
corresponding acid:
b/c pH = pK
a

when [HA] = [A

]
* Slope lower near midpoint

When [HA] = [A

],
pH is relatively insensitive to
addition of strong acid or base i.e.
buffered solution

Buffering capacity is maximal when pH =
pKa.

The useful range of a buffer is within one
pH unit of its pKa.
Above this, the pH will change rapidly.

* Slope lower near midpoint

When [HA] = [A

],
pH is relatively insensitive to
addition of strong acid or base i.e.
buffered solution.

Buffering capacity is maximal when pH =
pKa.

The useful range of a buffer is within one
pH unit of its pKa.
Above this, the pH will change rapidly.


Living Graph

Titration Curve for a Weak Acid

(5) Buffers

Buffer: A system whose pH changes only slightly
when small amounts of acid or base is added.

A buffer ordinarily consists of a weak acid and
its conjugate base, present in roughly equal amounts
(at pH = pKa of the acid)

Used to control the pH within a system

How buffer works? (Fig 2-19)
Buffer works because the added H
+
or OH

ions
are consumed and do not directly affect the pH.

HAc + OH

H
2
O + Ac

Ac

+ H
+
HAc


[buffer] >> added [H
+
]
or [OH

]
(6) The Henderson-Hasselbalch (H-H) Equation
The pH of a solution, and the concentration of an acid and its conjugate base are related
by the H-H equation:
[A

]
pH = pKa + log
[HA]

When the molar concentration of an acid (HA) and its conjugate base (A

) are equal ([A

]
= [HA]),
[A

]/[HA] = 1; and log[A

]/[HA] = log1 = 0
So the pH of the solution simply equals the pKa of the acid.

When [A

] > [HA], pH > pKa.

When [A

] < [HA], pH < pKa.

Derivation of the Henderson-Hasselbalch (H-H) Equation

From: K
a
= [H
+
][A

]/[HA], Solve for [H

+
], [H
+
] = K
a
[HA]/[A

]
Negative log of each side:
log [H
+
] = log K
a
log([HA]/[A

])
Convert to p scale: pH = pK
a
log([HA]/[A

])
Invert log: pH = pK
a
+ log([A

]/[HA])

[proton acceptor]
pH = pK
a
+ log
[proton donor]
Calculate the pH of a 2 L solution containing 10 mL of 5 M acetic acid (CH
3
COOH) and
10 mL of 1 M sodium acetate (CH
3
COONa). pK
a
of CH
3
COOH = 4.76.
Living Graph

Henderson-Hasselbalch Equation (Box 2.3)

(7) Polyprotic Acids:
Substances that have more than one acid/base group.

H
3
PO
4
H
2
PO
4

+ H
+
HPO
4
2
+ H
+
PO
4
3
+ H
+

pKa
1
= 2.14 pKa
2
= 6.86 pKa
3
= 12.4

Example: 1.00 mole of phosphoric acid (H
3
PO
4
) and 1.75 moles of NaOH are
added to 1 L of water. Calculate the pH.
Step 1: 1 mol of H
3
PO
4
+ 1.75 mol OH
-

1 mol H
2
PO
4
-
+ 1 mol H
2
O + 0.75 mol OH
-
Step 2: 1 mol of H
2
PO
4
-
+ 0.75 mol OH
-

0.25 mol H
2
PO
4
-
+ 0.75 mol HPO
4
2-
+ 0.75 mol H
2
O
Step 3: In the end, we have 0.25 moles of H
2
PO
4
-
and 0.75 moles of HPO
4
2-
,
we can calculate the pH using the H-H equation:
Step 4: Look up the pKa of the reaction:
pKa for H
2
PO
4
-
HPO
4
2-
+ H
+
, is 6.86
Step 5: Calculate [HA] = [H
2
PO
4
-
]: 0.25 mol/1 L = 0.25 M
Step 6: calculate [A-] = [HPO
4
2-
] : 0.75 mol/1 L = 0.75 M
Therefore: pH = pKa+ log[A-]/[HA]
= 6.86 + log((0.75 M)/(0.25 M)) = 7.34

Practice Questions
1. At 37
o
C, ion product for water (Kw) has a value
of 2.4 x 10
-14
.
What is the pH of pure water at 37
o
C? (6.81)

2. Hydroxide ions were released during an enzyme reaction performed at pH 6.8.
Circle the buffer you would select for the enzyme assay.
CH
3
COOH/CH
3
COO
-
pK
a
= 4.76
H
2
PO
4
-
/HPO
4
2-
pK
a
= 7.21
HCO
3
-
/CO
3
2-
pK
a
= 10.0

Example: The addition of a 0.01 mL drop of 1 M HCl to 1 L of water will change the
pH from 7 to 5. A small concentration of buffer can alter this so that there is
virtually no change in the pH, even with much larger amounts of acid added!

Q13, p.74.
A buffer contains 0.010 mol of lactic acid (pK
a
=3.86) and 0.050 mol of sodium
lactate per liter.
(a) Calculate the pH of the buffer.
(b) Calculate the change in pH when 5 mL of 0.5 M HCl is added to 1 L of the
buffer.
(c) What pH change would you expect if you added the same quantity of HCl to 1
L of pure water (pH=7).

Work on Q1, 2, 3, 5(c), 8, 9, 10, 11, 12, 14, 15, 16 (p.73-4).

(8) Biological buffers:

HCO
3

: H
2
CO
3
pKa = 6.35
HPO
4
2
: H
2
PO
4

pKa = 6.86

pKa of amino acid, histidine = 6.0
Common buffers used in lab:
Buffer pK
a
(25
o
C) Effective pH Range
succinate (pK
1
) 4.21 3.2-5.2
acetate 4.76 3.6-5.6
citrate (pK
2
) 4.76 3.0-6.2
malate (pK
2
) 5.13 4.0-6.0
succinate (pK
2
) 5.64 5.5-6.5
MES 6.10 5.5-6.7
carbonate (pK
1
) 6.35 6.0-8.0
citrate (pK
3
) 6.40 5.5-7.2
imidazole 6.95 6.2-7.8
MOPS 7.14 6.5-7.9
phosphate (pK
2
) 7.20 5.8-8.0
HEPES 7.48 6.8-8.2
Trizma (Tris) 8.06 7.5-9.0
glycine (pK
2
) 9.78 8.8-10.6
carbonate (pK
2
) 10.33 9.5-11.1




Bicarbonate Buffer System in Blood and Lung
* Slope lower near midpoint

When [HA] = [A

],
pH is relatively insensitive to
addition of strong acid or base i.e.
buffered solution

Buffering capacity is maximal when pH =
pKa.

The useful range of a buffer is within one
pH unit of its pKa.
Above this, the pH will change rapidly.

Why does the titration curve of a week acid look the way it looks?
Using the H-H equation, lets follow the change of pH as we increase the ratio of [acid]/[base].
[CH
3
COO

]
pH = pKa + log
[CH
3
COOH]
[CH
3
COO

]/[CH
3
COOH] log([CH
3
COO

]/[CH
3
COOH]) pH
1/10 log(1/10) = log10 = 1 4.76 1 = 3.76
1/4 log(1/4) = log4 = 0.602 4.76 0.602 = 4.16
1/2 log(1/2) = log2 = 0.301 4.76 0.301 = 4.46
3/4 log(3/4) = 0.125 4.76 0.125 = 4.64
1.0 log1 = 0 4.76
4/3 log(4/3) = 0.125 4.76 + 0.125 = 4.89
2/1 log2 = 0.301 4.76 + 0.301 = 5.06
4/1 log4 = 0.602 4.76 + 0.602 = 5.36
10/1 log10 = 1.0 4.76 + 1 = 5.76
and, so on....
From the H-H eq. we know that the pH is related to the ratio of [acid] and [conjugate base].
Since the relationship is logarithmic,
(1) ApH decreases as the ratio approaches to 1.0 (titration midpoint), and
(2) the titration curve is symmetrical on both sides of the midpoint.
Conclusion: A solution made of a weak acid and its conjugate base has its highest buffer
capacity at pH equal to its pKa.
(9) Water as a Reactant

Hydrolysis (exergonic)
are catalyzed by hydrolases.
( Condensation)