Water

and ionic equilibria

Chapter 2 Garrett and Grisham
Outline
Properties of Water
Unusual properties
Hydrogen bonding
Polar nature of water
Ionization of water
What is pH?
Strong/weak electrolytes
Hendersson/Hasselbalch
Titration curves
What are buffers?
Phosphate buffer/Histidine
Unique role of water in environment
Why are we talking about water
Water content of organisms varies between 70-90%
Cells are typically comprised of 70% water
Roles of water
Membrane formation
Folding of proteins, RNA and DNA
Enzyme mechanism
Heat conduction
Properties of water
Different properties than the corresponding hydrides of its
neighbors in the periodic table
The properties of water include
High boiling point
High melting point
High dielectric constant
Maximum density occurs in its liquid form, not solid
B C N O F
S
=> Intermolecular forces between water molecules are high
Structure of water
2 hydrogen atoms covalently attached to oxygen atom and sharing
electrons

4 electrons form 2 non-bonding pairs

Distorted tetrahedral arrangement (angle not 109.5 degrees)

=> Non linear arrangement
Structure of water
Dipole
moment
!
+
!
+

!
-

Hydrogen bonding in liquid water

Up to FOUR H-bonds (donates,
accepts)
Hydrogen bonding is
cooperative:
A H-bonded water molecule serving
as an acceptor is a better H-bond
donor
A H-bonded water molecule serving
as a donor is a better H-bond
acceptor
A
D
O
a
H
d
H
d
D
D
A
A
Average lifetime of hydrogen bond is 9.6
picoseconds (10
-12
)
constant reorganization of H-bond networks
disordered H-bonded network
strained, broken H-bonds: uidity
Hydrogen bonding in liquid water
Hydrogen bonding in ice
directional and straight:
strong bonds
The hydrogen and two
oxygens in the hydrogen
bond are linear

H-bond keeps water

molecules apart: open lattice
Ice has lower density than
liquid water
O H
H
O
2.8
0.96
1
2
3
4
5
6
6 H2O molecules linked
(hexagonal ice)
Solvation properties of water
Water is an excellent solvent for salts and polar compounds due to its highly
polar nature (or high dielectric constant)
Denition of dielectric constant
The dielectric constant of a solvent represents the reduction in energy of mutual
attraction between two charged species in vacuum relative to what it is in the
solvent: IT MEASURES THE POLARITY OF A SOLVENT
Solvents are classied in polar (water) and non-polar (hexane)
solvent
General rule: polar solvents dissolve polar compounds (sugars)
and non-polar solvents dissolve non-polar compounds (oil)
General rule: polar and non-polar solvents do not mix well
Interaction of water with polar and non-polar molecules
Polar molecules Non-polar molecules
Hydration shell
Hydrophobic interactions
Clustering of hydrophobic molecules reduces surface area that
interacts with water molecules (reduces ordered water molecules)
Result is: apparent afnity for hydrophobic molecules for each other
=> Hydrophobic interactions
Hydrophobic interactions drive protein folding
Amphiphilic (amphipathic) molecules
-
vdw
representation
shorthand
representation
Amphiphilic molecules
Amphiphilic molecules form three dimensional
structures when their concentration is high enough
Micelle Bilayer
Consequence for structure of water
Polar and non polar compounds force water
molecules to be more organized
Decrease the dynamic interplay between water
molecules
" Colligative properties: set of characteristic
changes in water properties including:
Freezing point depression, boiling point elevation,
vapor pressure lowering, osmotic pressure effect
Ionization of water
Formation of the hydronium ion is instantaneous (hydrogen bonds)
H
2
O HO
-
H
+
+
H
2
O H
+
+ H
3
O
+
Hydronium ion
Hydroxyl ion Hydrogen ion (proton)
Draw the hydration sphere of a hydronium ion
Draw the hydration sphere of a hydroxyl ion
K
w
, the ion product of water
10
-7
moles of H
+
or HO
-
are present in one liter of water at 25 C
The concentration of H
2
O in pure water is 55.5 M (moles/liter)
Dene a new constant, K
w
, the ion product of water, as
H
2
O H
+
+ OH
-

K
eq
=
[H
+
][OH
-
]
[H
2
O]
K
eq
= = 1.8 x 10
-16
M
(10
-7
)(10
-7
)
55.5
K
w
= 55.5 K
eq
= 1 x 10
-14
M
2
= [H
+
][OH
-
]
(equilibrium constant)
pH
pH = -log
10
[H
+
]
[H
+
][OH
-
] = 1 x 10
-14
M
2

pH [H
+
] [OH
-
]
0 1.0 10
-14
1 10
-1
10
-13
2 10
-2
10
-12
3 10
-3
10
-11
4 10
-4
10
-10
5 10
-5
10
-9
6 10
-6
10
-8
7 10
-7
10
-7
8 10
-8
10
-6
9 10
-9
10
-5
10 10
-10
10
-4
11 10
-11
10
-3
12 10
-12
10
-2
13 10
-13
10
-1
14 10
-14
1.0
log
10
[H
+
] + log
10
[OH
-
] = -14
-log
10
[H
+
] - log
10
[OH
-
] = 14
pH + pOH = 14 = pKw
pOH = -log
10
[OH
-
]
a
c
i
d
i
c

b
a
s
i
c

neutral
Denition
(in M at 25 degrees)
Time to think
Problem #1
Dissociation of strong electrolytes in water
Denition: Strong electrolytes completely dissociate in solution
Examples include NaCl, K
2
SO
4
, NaOH, and HCl

K
a
is the acid dissociation constant (in M)
For HCl, K
a
is 10
8
M (because [HCl] is very very small in aqueous
solution)
HCl + H
2
O H
3
O
+
+ Cl
-

K =
[H
3
O
+
][Cl
-
]
[H
2
O][HCl]
K
a
=
[H
+
][Cl
-
]
[HCl]
K
a
= K [H
2
O]
Proton transfer reaction
Equilibrium constant
[H2O]=55.5 M
(constant)
Time to think
Dissociation of strong electrolytes in water
The [H
+
] of a solution is equivalent to the [HCl] added to the
solution
Similarly, the [OH
-
] of a solution is equivalent to the [NaOH]
added to the solution
HCl H
+
+ Cl
-

NaOH Na
+
+ OH
-

Problem #2
Weak electrolytes in water
Denition: substances that only partially dissociate in water to form
ions are called weak electrolytes
Example: acetic acid (CH
3
COOH)
K
a
is also known as ionization constant (tendency to form ions)
The low value of acetic acid K
a
indicates that the protonated form of
acetic acid (HAc) predominates over the (conjugate) base form (Ac
-
)
CH
3
C
O
OH
CH
3
C
O
O
-

+ H
2
O
+ H
3
O
+

K
a
=
[H
+
][CH
3
CO
2
-
]
[CH
3
CO
2
H]
K
a
= 1.74 x 10
-5
M
(HAc) (Ac
-
)
Time to think
Problem #3
Henderson-Hasselbalch equation
The pH can be calculated with knowledge of the K
a
and the
concentrations of the weak acid HA and its conjugate base A
-

HA A
-
+ H
+

For K
a
=
[H
+
][A
-
]
[HA]
[H
+
] =
[A
-
]
K
a
[HA]
-log
10
[H
+
] = - log
10
[A
-
]
K
a
[HA]
-log
10
[H
+
] = - log
10
K
a
- log
10
[A
-
]
[HA]
pH = pKa + log
10
[HA]
[A
-
]
Denition: H-H equation describes dissociation of weak acid in presence
of its conjugate base
pKa= - log
10
K
a

When pH = pKa

If 100 ml of 0.1M acetic acid and 100 ml of 0.1M sodium acetate are
mixed, their pH will be equivalent to the pKa of acetic acid, i.e. 4.76
(Remember what Ka for CH
3
COOH is)
Similarly, if the pH of the solution is identical to the pKa, there will
be an equivalent amount of acid and conjugate base
If the pH < pKa, [HA] > [A
-
]
If the pH > pKa, [HA] < [A
-
]
HA A
-
+ H
+

pH = pK
a
+ log
10
[HA]
[A
-
]
If [A
-
] = [HA], then pH = pK
a

HA A
-
+ H
+

pKa
pH
Time to think
Problem #4
Titration curves
K
a
= 1.74. 10
-5
HAc Ac
-
+ H
+

Titration curves are used to determine

amount of acid in a solution
Measured volume of acid is titrated by
slowly adding a solution of a base (NaOH)
of known concentration
The pH is determined at each addition and
the pH value is plotted as a function of the
amount of OH- added: TITRATION
CURVE
Experimental method to determine pKa
K = [H2O]/[H+][OH-]=1/1.8.10
-16
=5.5.10
15
H
+
+ OH
-
H
2
O
[Hac]=[Ac
-
]
Time to think
Problem #5
Phosphoric acid (H
3
PO
4
)
P
O
OH
OH
HO P
O
OH
OH
O P
O
OH
O
O P
O
O
O
O
-
-
- -
-
-
Polyprotic acid (3 dissociable
protons)
Requires 3 equivalent of OH- to
neutralize it
Each dissociation has a specic
pKa
Time to think
Problem #6
Buffers
Buffers resist changes in pH when H
+
or OH
-
is added
Buffer systems are typically comprised of a weak acid and its
conjugate base
Components of a buffer system are chosen such that the pKa of
weak acid is close to pH of interest.
Physiological buffers
Structure, function and activity of proteins is sensitive to pH
pH of extracellular uid is 7.4
Regulated by the bicarbonate system
The intracellular pH of most cells is found between 6.9 and 7.4
Phosphate system and histidine system used to buffer cell pH
(gastric uid)
(small intestine) (tears)
Phosphate buffer system
The phosphate system buffers intracellular uid of cells at pK
2

Phosphate is abundant in cells, existing in an inorganic form and

as a functional group on organic molecules
P
O
OH
OH
O P
O
O
O
-
-
-
OH
pK
2
= 7.2

Histidine-imidazole group
Histidine
one of the twenty amino acids that make up protein polymers.
Imidazole ring is responsible for buffering capacity
HN N
H
+
CH
2
C
CO
2
-

H
3
N
H
+
HN
N
CH
2
C
CO
2
-

H
3
N
H
+
N N
H
+
pK
a
= 7.0
N N
H
H
Imidazole
Histidine
pK
a
= 6.0
N N
H
+
CH
2
CH
CO
2
-

H
3
N
+
CH
2
CH
2
C
O
N Anserine
pK
a
= 7.0
CH
3

Buffers used in research

N N
HO CH
2
CH
2

CH
2
CH
2
S OH
Hepes
N N
HO CH
2
CH
2

+
H CH
2
CH
2

O
O
S O
O
O
- Protonated form
at pH 7.4
pKa=3
pKa=7.55
Things you should know
Properties of water: structure, H-bonding, solvation
Ionization of water, Kw, pH
Dissociation of strong electrolytes in water: Ka, pKa
Dissociation of weak electrolytes in water
Henderson-Hasselbalch equation
Ci. Vi = Cf. Vf
Titration curves
Buffers

Things to do
Read Chapter 2 in Garrett and Grisham ((including the "Bicarbonate Buffer
system of Blood Plasma")
Problems 1-7, 10, 11, 13, 15, 16, 18, 19, 20