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15.

1 Water and Its Properties >

Chapter 2
Water and Aqueous Systems

2.1 Water and Its Properties

2.2 Ionic Equilibria

2.3 Buffering Against pH Changes


in Biological Systems

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15.1 Water and Its Properties >

Objectives:
• relate the properties of water to its role in
biological systems;
• describe how simple ions and molecules
behave in aqueous environment; and
• identify important biological buffers and their
uses in biological systems.

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15.1 Water and Its Properties > CHEMISTRY & YOU

What properties of water make it essential to life on


Earth?

• Water covers about three


quarters of Earth’s surface. All
known life forms are made
mostly of water.
• The chemical and physical
processes of life require that
molecules be able to move
about, encounter one another,
and change partners frequently
in the complicated processes of
metabolism and synthesis.
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15.1 Water and Its Properties > Water in the Liquid State

Water in the Liquid State


•The processes of life require a wide variety of ions
and molecules to move about in proximity, that is, to
be soluble in a common medium.
•Water serves as the universal intracellular and
extracellular medium and an excellent solvent
because of its hydrogen-bonding potential and its
polar nature.

What factor causes the high surface tension, low


vapor pressure, and high boiling point of water?

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15.1 Water and Its Properties > Water in the Liquid State

Water, H2O, is a simple molecule


consisting of three atoms.
• The oxygen atom forms a covalent bond
with each of the hydrogen atoms.

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15.1 Water and Its Properties > Water in the Liquid State

Water, H2O, is a simple molecule


consisting of three atoms.
• The oxygen atom forms a covalent bond
with each of the hydrogen atoms.
• Oxygen has a greater electronegativity
than hydrogen, so the oxygen atom attracts
the electron pair of the covalent O—H bond
to a greater extent than the hydrogen atom.

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15.1 Water and Its Properties > Water in the Liquid State

Water, H2O, is a simple molecule


consisting of three atoms.
• The oxygen atom forms a covalent bond
with each of the hydrogen atoms.
• Oxygen has a greater electronegativity
than hydrogen, so the oxygen atom attracts
the electron pair of the covalent O—H bond
to a greater extent than the hydrogen atom.
• Thus, the O—H bond is highly polar.

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15.1 Water and Its Properties > Water in the Liquid State

• The oxygen δ– δ–

atom acquires a
partial negative
charge (δ–). δ+ δ+
Polar bonds Molecule has net polarity
δ– δ–

δ+ δ+

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15.1 Water and Its Properties > Water in the Liquid State

• The oxygen δ– δ–

atom acquires a
partial negative
charge (δ–). δ+ δ+
Polar bonds Molecule has net polarity
• The less δ– δ–

electronegative
hydrogen atoms δ+ δ+
acquire partial
positive charges
(δ+).
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15.1 Water and Its Properties > Water in the Liquid State

How do the polarities of the two O—H


bonds affect the polarity of the molecule?
δ– δ–

δ+ δ+
Polar bonds Molecule has net polarity
δ– δ–

δ+ δ+

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15.1 Water and Its Properties > Water in the Liquid State

How do the polarities of the two O—H


bonds affect the polarity of the molecule?
δ– δ–
• The molecule
has a bent
shape.
δ+ δ+
Polar bonds Molecule has net polarity
δ– δ–

δ+ δ+

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15.1 Water and Its Properties > Water in the Liquid State

How do the polarities of the two O—H


bonds affect the polarity of the molecule?
δ– δ–
• The molecule
has a bent
shape.
δ+
• The two O—H δ+

bond polarities Polar bonds Molecule has net polarity


δ– δ–
do not cancel.

δ+ δ+

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15.1 Water and Its Properties > Water in the Liquid State

How do the polarities of the two O—H


bonds affect the polarity of the molecule?
δ– δ–
• The molecule
has a bent
shape.
δ+
• The two O—H δ+

bond polarities Polar bonds Molecule has net polarity


δ– δ–
do not cancel.
• The water
molecule as a δ+ δ+
whole is polar.
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15.1 Water and Its Properties > Water in the Liquid State

In general, polar molecules are attracted


to one another by dipole interactions.
• The negative end of
δ+ one molecule attracts
the positive end of
another molecule.
δ–

δ+

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15.1 Water and Its Properties > Water in the Liquid State

However, in water, this attraction results


in hydrogen bonding.
• Hydrogen bonds are attractive forces that
arise when a hydrogen atom is covalently
bonded to a very Hydrogen
bond
electronegative
atom and also
weakly bonded to an
unshared electron
pair of another
electronegative
Liquid water
atom.
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15.1 Water and Its Properties >

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15.1 Water and Its Properties > Water in the Liquid State

Many unique and important


properties of water—including
its high surface tension, low
vapor pressure, and high
boiling point—result from
hydrogen bonding.

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15.1 Water and Its Properties > Water in the Liquid State

Surface Tension
Have you ever noticed that water forms
nearly spherical droplets on a leaf?

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15.1 Water and Its Properties > Water in the Liquid State

Surface Tension
• The water molecules within the body of the liquid
form hydrogen bonds with the other molecules that
surround them on all sides.
• The attractive forces on each of
these molecules are balanced.

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15.1 Water and Its Properties > Water in the Liquid State

Surface Tension
• The water molecules within the body of the liquid
form hydrogen bonds with the other molecules that
surround them on all sides.
• The attractive forces on each of
these molecules are balanced.
• Water molecules at the surface
of the liquid experience an
unbalanced attraction.
• As a result, water molecules at
the surface tend to be drawn
inward.
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15.1 Water and Its Properties > Water in the Liquid State

Surface Tension
The inward force, or pull, that tends to
minimize the surface area of a liquid is
called surface tension.

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15.1 Water and Its Properties > Water in the Liquid State

Surface Tension
The inward force, or pull, that tends to
minimize the surface area of a liquid is
called surface tension.
• All liquids have a surface tension, but
water’s surface tension is higher than most.
• The surface tension of water tends to hold a
drop of liquid in a spherical shape.

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15.1 Water and Its Properties > Water in the Liquid State

Surface Tension
It is possible to decrease the surface
tension of water by adding a surfactant.
• A surfactant is any substance that
interferes with the hydrogen bonding
between water molecules and thereby
reduces surface tension.

• Soaps and detergents are surfactants.

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15.1 Water and Its Properties > Water in the Liquid State

Vapor Pressure
Hydrogen bonding between water
molecules also explains water’s unusually
low vapor pressure.

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15.1 Water and Its Properties > Water in the Liquid State

Vapor Pressure
Hydrogen bonding between water
molecules also explains water’s unusually
low vapor pressure.
• An extensive network of hydrogen bonds holds
the molecules in liquid water to one another.
• These hydrogen bonds must be broken before
water changes from the liquid to the vapor
state, so the tendency of these molecules to
escape is low and evaporation is slow.
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15.1 Water and Its Properties > Water in the Liquid State

Boiling Point
Molecular compounds of low molecular
mass are usually gases or liquids with
low boiling points at normal atmospheric
pressure.
• Ammonia (NH3) has a molar mass of
17.0 g/mol and boils at about –33˚C.

• Water has a molar mass of 18.0 g/mol,


but it has a boiling point of 100˚C.
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15.1 Water and Its Properties > Water in the Liquid State

Boiling Point
The difference between the boiling points
of ammonia and water is due to hydrogen
bonding, which is more extensive in water
than in ammonia.
• It takes much more heat to disrupt the
attractions between water molecules
than those between ammonia molecules.

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15.1 Water and Its Properties >

Some insects are able to walk across


water. How do the properties of water
explain their ability?

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15.1 Water and Its Properties >

Some insects are able to walk across water.


How do the properties of water explain their
ability?
The surface tension of
water is relatively high. As
long as the forces holding
the surface water
molecules together are
stronger than the forces
exerted down on the water
by the insect, the insect will
not sink.
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15.1 Water and Its Properties > Water in the Solid State

Water in the Solid State


How can you describe the
structure of ice?

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15.1 Water and Its Properties > Water in the Solid State

Ice cubes float in your glass of iced tea


because solid water has a lower density
than liquid water.
• This situation is not usual for liquids.

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15.1 Water and Its Properties > Water in the Solid State

As water begins to cool, it behaves


initially like a typical liquid.
• It contracts slightly, Density of Liquid Water and Ice
and its density Temperature (˚C) Density (g/cm3)
gradually increases. 100 (liquid water) 0.9584
50 0.9881
• When the 25 0.9971
temperature of the 10 0.9997
water falls below 4 1.0000

4˚C, the density of 0 (liquid water) 0.9998


0 (ice) 0.9168
water actually starts
to decrease.
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15.1 Water and Its Properties > Water in the Solid State

Below 4˚C, water no longer behaves


like a typical liquid.
• Ice, which forms at Density of Liquid Water and Ice
0˚C, has about a Temperature (˚C) Density (g/cm3)
10% lower density 100 (liquid water) 0.9584

than water at 0˚C. 50 0.9881


25 0.9971
• Ice is one of only a 10 0.9997

few solids that 4 1.0000


0 (liquid water) 0.9998
floats in its own
0 (ice) 0.9168
liquid.

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15.1 Water and Its Properties > Water in the Solid State

Why is ice less dense than liquid water?

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15.1 Water and Its Properties > Water in the Solid State

Why is ice less dense than liquid water?


The structure of ice is a regular open
framework of water molecules in a
hexagonal arrangement.

The hexagonal
symmetry of a
snowflake reflects the
structure of the ice
crystal.

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15.1 Water and Its Properties > Water in the Solid State

The unique properties of ice are a result


of hydrogen bonding.
• Extensive hydrogen
bonding in ice holds
Hydrogen
bond the water molecules
farther apart in a
more ordered
arrangement than in
liquid water.
Ice
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15.1 Water and Its Properties > Water in the Solid State

The fact that ice floats has important


consequences for all organisms.
• The liquid water at the bottom of an
otherwise frozen body of water is warmer
than 0˚C, so fish and other aquatic life are
better able to survive.
• If ice were denser than liquid water,
bodies of water would tend to freeze solid
during the winter months, destroying
many types of organisms.

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15.1 Water and Its Properties > CHEMISTRY & YOU

What properties of water that result from hydrogen


bonding make it essential to life on Earth?

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15.1 Water and Its Properties > CHEMISTRY & YOU

What properties of water that result from hydrogen


bonding make it essential to life on Earth?

• The low vapor pressure of water keeps the liquid


water in all of Earth’s lakes and oceans from
evaporating rapidly.
• If water did not have such a high boiling point, it
would be a vapor at the usual temperatures
found on Earth.
• The fact that ice floats allows fish and other
aquatic life to survive the winter months.
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15.1 Water and Its Properties >

In ice, how many hydrogen bonds can


be formed between one hydrogen atom
of a water molecule and the oxygen in
surrounding water molecules?

A. 0
B. 1
C. 2
D. 3
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15.1 Water and Its Properties >

In ice, how many hydrogen bonds can


be formed between one hydrogen atom
of a water molecule and the oxygen in
surrounding water molecules?

A. 0
B. 1
C. 2
D. 3
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15.1 Water and Its Properties > Key Concepts

Many unique and important


properties of water—including its high
surface tension, low vapor pressure,
and high boiling point—result from
hydrogen bonding.

The structure of ice is a regular open


framework of water molecules in a
hexagonal arrangement.

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15.1 Water and Its Properties > Glossary Terms

• surface tension: an inward force that


tends to minimize the surface area of a
liquid; it causes the surface to behave
as if it were a thin skin
• surfactant: any substance that
interferes with the hydrogen bonding
between water molecules and thereby
reduces surface tension; soaps and
detergents are surfactants

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15.1 Water and Its Properties > BIG IDEA

Bonding and Interactions


• Water molecules are held together through
hydrogen bonds.
• The hydrogen bonding interactions between
water molecules account for the unique
properties of water, including its high surface
tension, low vapor pressure, and high boiling
point.
• Hydrogen bonding also accounts for the fact
that ice is less dense than liquid water.

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15.1 Water and Its Properties >

Water has a high specific heat


• Specific heat is the amount of heat needed
to raise or lower 1 g of a substance by 1 oC.
• Water can resist temperature change for
heating and cooling.
• Water absorbs or releases large amounts of
heat energy with little change in actual
temperature.

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15.1 Water and Its Properties >

Water has a high heat of vaporization


• The heat of vaporization is the energy
needed to convert 1g of a substance from
liquid to gas.
• In order for water to evaporate, bonds must
be broken.
• As water evaporates, it removes a lot of heat
with it.

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15.1 Water and Its Properties >

Water has a high thermal conductivity


• Water expands as it freezes, unlike other
liquids resulting in it becoming less dense as
a solid than as a liquid.
• The hydrogen bonds in liquid water are
constantly being broken and reformed.
• Water that is frozen forms a crystal-like
lattice whereby molecules are set at fixed
distances.
• This explains why ice floats on water.

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15.1 Water and Its Properties >
IONIC EQUILIBRIA
• Most biochemical reactions occur in an aqueous
environment; the exceptions are those that occur within
the hydrophobic interiors of membranes.
• The many substances dissolved in the aqueous cytosol
and extracellular body fluids include free ions like K+, Cl-,
and Mg2+, as well as molecules and macromolecules
carrying ionizable groups.
• The behavior of all these molecules in biochemical
processes depends strongly on their state of ionization.
• Thus, it is important that we review briefly some aspects
of ionic equilibrium, particularly acid–base equilibria and
the ionization of water.

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15.1 Water and Its Properties >

• Ionic Equilibrium is the condition in which the


rate of dissociation of nonionized molecules is
equal to the rate of combination of the ions.
• It is also the equilibrium established between the
unionized molecules and the ions in the solution
of weak electrolytes.
• Electrolytes are compounds that ionize (or
dissociate into their constituent ions) to produce
aqueous solutions that conduct an electric
current; while nonelectrolytes exist as molecules
in aqueous solution, and such solutions do not
conduct an electric current.
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15.1 Water and Its Properties > Ionic Equilibrium

• Strong electrolytes almost completely ionized in solution,


such as table salt (NaCl); while weak electrolytes do not
completely dissociate or only partially ionize in aqueous
solution (usually 1% to 10%), such as acetic acid.
• Electrolytes may be acids, bases or salts.
• Acids are sour in taste and known to turn blue litmus paper into
red. They liberate dihydrogen on reacting with metals. Examples
are Sulfuric acid (H2SO4), Acetic acid (CH3COOH), and Carbonic
acid H2CO3.
• Bases are bitter in taste and are known to turn red litmus paper to
blue. Examples of bases include Sodium hydroxide (NaOH),
Potassium hydroxide (KOH), and Calcium hydroxide (Ca(OH)2.
• Salts are formed when an acid is neutralized by a base. These
contain a metal part (cation) and non-metal (anion). Examples
include Sodium chloride (NaCl), Sodium sulfate (Na2SO4), and
Ammonium nitrate (NH4NO3).
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15.1 Water and Its Properties > ACIDS

• An acid is any hydrogen


containing substance that is
capable of donating a proton
or hydrogen ion to another
substance.
Arrhenius definition:
• Any substance that, when
dissolved in water, increases
the concentration of
hydronium ion (H3O+) is
called an acid.
• Thus acids are proton donors
or electron acceptors.

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15.1 Water and Its Properties >
BASES
• Bases taste bitter
• Bases are slippery or soapy to touch
• Bases can turn acidified red litmus to blue
• Their aqueous solutions conduct electric current
• Bases react with acids to form salts and water
• A strong base can release hydroxyl ions in maximum
amount. Common examples of strong bases include
hydroxides of alkali metals and alkaline earth metals
like NaOH and Ca(OH)2.

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15.1 Water and Its Properties >
Formation of Salts

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15.1 Water and Its Properties >
The pH Scale
The ion product of water, KW, is the
basis for the pH scale (Table 2-6). The
pH scale is a convenient way of
designating the concentrations of H+
and OH- in solution in the range
between 1.0 M H+ and 1.0 M OH-. The
pH is defined by the equation
pH = -log [H+].
A precisely neutral solution occurs
when [H+] = [OH-], and thus when pH =
7.0. Solutions in which [H+] > [OH-] are
acidic and have pH values less than
7.0. Solutions in which [H+] < [OH-] are
basic and have pH values greater than
7.0.

54
15.1 Water and Its Properties >
pH Values of Some Common Liquids
The pH values of some common
aqueous fluids are shown in Fig. 2-15.
Remember that the pH scale is
logarithmic, and solutions that differ by
one pH unit actually differ by 10-fold in
[H+]. The [H+] of a solution of known pH
is calculated by rearranging the pH
equation to its exponential form:
[H+] = 10-pH.
The pH of biological solutions is
carefully controlled because pH
strongly affects the structure and
activity of biological macromolecules,
e.g., enzymes.
55
15.1 Water and Its Properties > ACIDS AND BASES

PROTON DONORS AND ACCEPTORS


• Bronsted-Lowry Theory is also called “Proton Theory” of acids
and bases. This theory was introduced independently in 1923
by the Danish chemist Johannes Nicolaus Bronsted and the
English chemist Thomas Martin Lowry. Bronsted-Lowry Theory
states that any compound that can transfer a proton to any
other compound is an acid, and the compound that accepts
the proton is a base.
• It is based on the compounds abilities to either donate or
accept protons. A Bronsted-Lowry acid is proton (hydrogen-
ion) donor and a Bronsted-Lowry base is a proton
(hydrogen ion) acceptor.
• A strong acid dissociates almost completely into a proton and
a weak conjugate base, while a strong base ionizes entirely,
releasing OH- ion, which is a powerful proton acceptor.
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15.1 Water and Its Properties >

IONIZATION OF WATER AND THE ION PRODUCT

• Although water is essentially a neutral molecule, it


does have a slight tendency to ionize; in fact, it
can act as both a very weak acid and a very weak
base.
• The most correct way to understand this ionization
reaction is to note that one water molecule can
transfer a proton to another to yield a hydronium
ion (H3O+) and a hydroxide ion (OH-) so that water
is both the proton donor and the proton acceptor.

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15.1 Water and Its Properties >
IONIZATION OF WATER AND THE ION PRODUCT

A proton never exists in aqueous solution as a free ion—it is


always associated with one or more water molecules.
Whenever we write a reaction involving aqueous H+, we
are really referring to a hydrated proton.

The equilibrium can be expressed in terms of Kw, the ion


product of water, which is 10-14 at 25 °C:

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15.1 Water and Its Properties >

IONIZATION OF WATER AND THE ION PRODUCT

• In pure water to which no acidic or basic substances


have been added, all the H+ and OH- ions must come
from the dissociation of the water itself. Under these
circumstances the concentrations of H+ and OH- must be
equal; thus, at 25 °C,

• and the solution is said to be neutral, that is, neither


acidic nor basic.
• The product of concentrations of hydrogen and hydroxyl
ions is a constant at a given temperature.

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15.1 Water and Its Properties >

The pH scale
• means "power of hydrogen"
• measures the concentration of H+ (H3O+) ions,
[H+] in solution used to make the wide range
of possible concentrations easier to work with
• pH is a mathematical scale in which the
concentration of hydronium ions in a solution
are expressed as a number from 0 to 14 (a
logarithmic scale of 100 to 10-14)

60
15.1 Water and Its Properties > The pH scale (cont)

The value of pH is the negative of the


exponent,
i.e.: 0 to 14

ex. If [H+] is 10-6 M, the pH is 6

If pH = 12, then [H+] = 10-12 M

61
15.1 Water and Its Properties > The pH scale (cont)

pH can be used to determine pOH


("power of hydroxide")
ex. If pH = 12, then pOH = 2

**pOH will be the difference between 12 and 14


(the high end of the pH scale) :
pH + pOH = 14**
If pH = 12, then [OH-] = 10-2 M

62
15.1 Water and Its Properties >
pH scale

the pH value can be calculated on calculator


using the logarithmic function

pH= -log[H+] [H+] = hydrogen ion


concentration

pOH =-log[OH] [OH] = hydroxide ion


concentration

pH + pOH = 14 (at 25ºC)

63
15.1 Water and Its Properties >

#1 To find the pH you must take the –log[H+]


#2 To find the pOH you must take the –log[OH-]
#3 To find the [H+] you must take the anti-log of the
pH
4# To find the [OH-] you must take the anti-log of the
pOH
https://www.youtube.com/watch?v=LS67vS10O5Y

64
15.1 Water and Its Properties >

pH Practice problems

1) hydronium ion = 10-5 M


pH= -log[10-5] = 5 pOH = 9

2) hydroxide ion = 10-4 M


pOH= -log[10-4] = 4 pOH = 4

65
15.1 Water and Its Properties >

pH Practice problems
3) hydroxide ion = .01 M
pH= -log[10-0.01] = 2 pOH = 12

4) hydroxide ion = .056 M


pH= -log[10-0.056] = 1.25 pOH = 14-1.25 = 12.75

5) hydroxide ion = .0076 M


pH= -log[10-0.0076] = 2.11 pOH = 14-1.25 = 11.89

66
15.1 Water and Its Properties >

Calculation of [H+]

67
15.1 Water and Its Properties >
Calculation of [OH-]

68
15.1 Water and Its Properties >

The pH Scale and the Physiological pH Range


• pH is a measure of hydrogen ion concentration or the
acidity or alkalinity of a solution.
• Aqueous solutions at 25°C with a pH less than seven are
acidic, while those with a pH greater than seven are basic
or alkaline.
• The pH of a solution is most conveniently measured with
glass electrode pH meters. The electrode generates an
electrical potential, which depends on the H+ concentration;
this is converted by the instrument into a pH reading.
• Most body fluids have pH values in the range 6.5–8.0,
which is often referred to as the physiological pH range.
• Most biological reactions occur between pH 6.5 and pH 8.0.

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15.1 Water and Its Properties >

Buffers are Mixtures of Weak Acids and their


Conjugate Bases

• Buffers are aqueous systems that tend to resist changes


in pH when small amounts of acid or base are added. A
buffer system consists of a weak acid (the proton donor)
and its conjugate base (the proton acceptor).
• Whenever H+ or OH- is added to a buffer, the result is a
small change in the ratio of the relative concentrations of
the weak acid and its anion and thus a small change in
pH. The decrease in concentration of one component of
the system is balanced exactly by an increase in the
other. The sum of the buffer components does not
change, only their ratio.

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15.1 Water and Its Properties >
Buffers are Mixtures of Weak Acids and their Conjugate
Bases

• Buffered solutions are able to minimize the change in pH


following addition of H+ or OH- because the conjugate acid
(HA) and conjugate base (A-) of the buffering compound
(commonly called the buffer or buffer salt) are present in
sufficient concentration to combine with the added H+ or
OH- and neutralize them:

• When an acid transfers a proton to a base, the acid is converted


to its conjugate base.
• When a base accepts a proton, it is converted to its conjugate
acid.

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15.1 Water and Its Properties >
THE HENDERSON-HASSELBALCH EQUATION
RELATES PH, pKa AND BUFFER CONCENTRATION

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15.1 Water and Its Properties >

BIOLOGICAL BUFFERS
• The intracellular and extracellular fluids of
multicellular organisms have a characteristic
and nearly constant pH.
• The organism’s first line of defense against
changes in internal pH is provided by buffer
systems.

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15.1 Water and Its Properties >

BIOLOGICAL BUFFERS

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