CHAPTER 2
THE AQUEOUS ENVIRONMENT OF THE PROTOPLASM
INTRODUCTION
Water is the most abundant liquid in the world and the most abundant substance in living
systems. The water content of living organisms varies from less than 50% in bacterial cells to
about 96% in some marine invertebrates. The human body contains from 60 to 70% water which
is found within the cells, in the extracellular fluid that bathes the cell, and in the blood plasma.
Man cannot survive for more than a few days without water.
To understand the chemistry of living organisms, we need to examine the properties of
water that make it so essential for life.
LEARNING OUTCOMES
At the end of this unit, you should be able to:
enumerate the properties of water that make it suited for biological systems
discuss the Bronsted-Lowry definition of acids and bases
state the difference between strong acids and weak acids, between strong bases and
weak bases
calculate the [H+][OH-], and pH of aqueous solutions of weak acids and bases
explain how buffers operate
LEARNING CONTENTS
1. PROPERTIES OF WATER
Solvent Properties
Water is by far the most abundant molecule found in organisms. It possesses unique
chemical properties that suit it admirably for biological systems. Most of these properties are
derived from the polarity and H-bonding ability of water molecules.
Because of the electronegativity of oxygen and the bond angle between the two H atoms,
the water molecule is polar, with one end partially negatively charged and the other end partially
positively charged as shown in Fig. 2-1.
Figure 2-1. Polarity of H2O molecule
Consequently, water is an excellent solvent for polar substances and conveniently forms
hydrated micelles with non-polar substances. It is called the universal solvent because it is a
better solvent than most other liquids.
The molecules of water are extensively H-bonded, resulting in other special properties of
water compared to other hydrides as shown in Table 2-1.
Table 2-1. Some physical properties of hydrides
Hydride M.P. °C B.P. °C Heat of vaporization
(cal/g)
H2O 0 100 540
H2S -85 -60 132
NH3 -78 -33 327
High Melting and Boiling Points
Water has a high melting point and a high boiling point when compared to other
hydrides. In fact, most hydrides are gases at the temperature that water is a liquid. Due to the H-
bonds between water molecules, more energy is required to pull these molecules apart.
High Heat of Vaporization
Water has a high heat of vaporization. It is important to realize that evaporation is
essentially the same process as boiling. It involves changing liquid water to gas, only at a
slower rate. Like boiling, evaporation uses up a great deal of energy or heat.
High Heat of Fusion
Water has a high heat of fusion (80 cal/g). It means a great deal of heat must be released
before ice can be formed.
High Specific Heat
The specific heat of a liquid is the amount of heat required to raise the temperature of one
gram of that liquid 1oC (like for example from 15° to 16°C). Water has a high specific heat
compared to other liquids. (Sp heat of water is 1 cal/gram oC)
Density of Ice
Water is most dense at 4°C. As it continues to cool and then freeze at 0°C, it expands by
9%. It is the open lattice structure of ice, (Fig. 2-2) in which each molecule of water is bonded to
four other water molecules, that makes ice less dense than the more compact liquid water.
Figure 2-2. The structure of ice
2. IONIZATION OF WATER
Ionization of Water
The highly polar nature of water suggests that water ionizes, and it does in the following
manner:
H2O H+ + OH-
Hydrogen ions (H+) in aqueous solution have several other names such as protons,
hydronium ions (H3O+) or solvated protons since H+ are always joined to water molecules in
aqueous solutions. In this module we use either H+ or H3O+ to represent hydrogen ions.
The self-ionization of water occurs only to a very small extent. In pure water of 25°C the
hydrogen ion concentration [H+] and the hydroxyl ion concentration [OH-] are each only
0.0000001 M or 1.0 x 10-7 M. Note that in pure water these ions are produced in a 1:1 ratio. An
aqueous solution wherein [H+] = [OH-] = 1.0 x 10-7 M is described as a neutral solution.
The product of the concentrations of the hydrogen ions and hydroxyl ions in water is Kw,
the equilibrium constant for aqueous system. Its value is 1.0 x 10-14 at 25°C.
In an aqueous solution the [H+] and [OH-] are interdependent. If the H+ increases, then the [OH-]
decreases and vice versa. Just like any system in equilibrium, Le Chatelier’s principle applies
here. If additional ions either [H+] or [OH-] are added to the solution, the equilibrium will shift to
decrease the other type of ion. More water molecules are formed in the process.
H+ + OH- H2O
When a substance that releases hydrogen ions is dissolved in water the [H+] inevitably
increases and becomes greater than the [OH -]. The solution ceases to be neutral. When the [H+] >
[OH-] the solution is described as an acidic solution.
One substance that can make the solution acidic is hydrogen chloride which dissolves in
water to form hydrochloric acid
water
HCl (g) ------------ H+ (aq) + Cl- (aq)
When sodium hydroxide on the other hand, is dissolved it donates hydroxyl ions (OH-) to the
solution.
water
NaOH(s) ------------- Na+ (aq) + OH- (aq)
In this case [H+] < [OH-]. This condition gives rise to a basic solution.
It should be kept in mind that H + and OH- will always be present in aqueous solutions,
even those of acids and bases. The said H + and OH- are present for the self-ionization of water. If
we know the concentration of one of the ions we can always find the concentration of the other
using Kw.
The pH concept
The expression of very small [H+] in moles/liter or Molarity (M) is cumbersome. A more
widely used system is the pH scale. It was proposed by the Danish scientist Soren Sorensen in
1909.
The pH of a solution is the negative logarithm of the [H+].
pH = - log [H+]
In a neutral solution the [H+] = 1 x 10-7 M. The pH of a neutral solution is 7.
For pH calculations, concentrations should be expressed in exponential form. For
example, a [H+] of 0.01 M is rewritten as 1 x 10 -2M. Its pH is 2.0. A pH of 0 is strongly acidic.
A pH of 14 is strongly basic.
In similar way pOH equals the negative logarithm of the [OH-]
pOH = -log [OH-]
However, the practice is to express the pH for both acids and bases. If the pH is known,
then the pOH is easily determined since
pH + pOH = 14
● Neutral solution : pH = 7; [H+] = 1 × 10-7 M.
● Acidic solution : pH is less than 7; [H+] is greater than 1 x 10-7 M.
● Basic solution : pH is greater than 7.0; the [H+] is less than 1x10-7 M.
Table 2.2 Relationship between the [H+], the [OH-], and pH
Table 2-2 gives the pH values of a number of common aqueous solutions. The pH scale is
a convenient expression of the [H+] of biological systems. The Table also summarize the
relationships between [H+], [OH-], and pH.
3. THE BRONSTED-LOWRY DEFINITION OF ACIDS AND BASES
Acids and bases are defined in three different ways by three different scientists.
Arrhenius, Bronsted and Lowry, and Lewis based on their respective definitions on their
laboratory exercises with these substances. The definition of Bronsted and Lowry is the most
convenient for acids and bases in living organisms.
An acid is a substance that can donate a proton, H+.
A base is a substance that can accept a proton, H+.
Let us look at an example:
HNO2 + H2O NO2- + H3O+
Acid Base1 Conjugate Base Conjugate Acid
In this reaction nitrous acid, HNO2 is donating a proton to water. Therefore, HNO 2 is the
acid and water acts as the base. In the reverse reaction, the hydronium ion, H3O+, is the acid and
the nitrite ion, NO2- , is the base.
This is a useful concept in biochemistry because many biomolecules are capable of
donating or accepting protons and they influence the [H+] in biological systems.
The Strength of Acids and Bases
There are 2 classes of acids:
1. Strong acids – completely donate their protons in water or they are completely ionized in
water. HCl and H2SO4 are examples of strong acids.
2. Weak acids – only partly ionize in water to donate protons. Organic acids are weak acids.
Living organisms have plenty of organic acids. Let us therefore consider the ionization of
one such acid: acetic acid, CH3COOH. Mathematically, the strength of a weak acid can be
determined from its ionization constant, Ka. The ionization of acetic acid can be represented by
the equation.
CH3COOH CH3COO- + H+
Then Ka is given by the equation
[H+] [CH3COO -]
Ka = -------------------------
[CH3COOH]
Problem: If Ka of acetic acid is 1.8 x 10-5 at 25°C, what is the
a. [H+] of a 1M acetic acid solution?
b. pH of the solution
To solve the problem
Given: conc. Acetic acid = 1M
a. Let x = [H+] = [CH3COO-]
From the value of Ka which 1.8 x 10-5, it can be deduced that x <<1 so that it can be
assumed that
[CH3COOH] ~ 1M
[CH3COOH] CH3COO- + H+
(1 – x) ~ 1 x x
To calculate for x, use the Ka expression for CH3COOH.
Ka = (x) (x)
1
1.8 x 10 = x2
-5
x = 4.24 x 10-3 M = [H+]
b. pH = -log[H+]
= -log (4.24 x 10-3)
pH = 2.37
Henderson-Hassellbalch Equation
For a better appreciation of the role of weak acids in living systems, the equilibrium expression
is written in another form, called the Henderson-Hassellbalch equation. It is obtained as
follows:
1. Inside the general expression HA H+ + A- so
2. Rearrange the Ka expression to solve for [H+]
3. Invert to logarithmic functions
4. Make the expression negative
5. Define –log [H+] as OH and –log Ka as pKa and convert
to
6. Henderson-Hassellbalch equation
4. BUFFER SYSTEMS
What are Buffers?
Buffers are solutions in which the pH remains relatively constant when small amounts of
acid or base are added. A buffer is a solution of a weak acid and one of its salt. It could also be a
solution of a weak base and one of its salts. The acetic acid – sodium acetate combination
given in the previous section is a typical example of a buffer system. Acetic acid and its anion,
CH3COO- act as reservoirs of neutralizing power. The acetic acid contains mostly undissociated
CH3COOH which is capable of reacting with an added base by furnishing H +, thereby
counteracting the effect of added base.
Consider the buffer system: CH3COOH --- CH3COO-
When a basic solution example NaOH is added, the acid will react with the base
-
CH3COOH + OH ---------> CH3COO- + H2O
Acid base conjugate base conj acid
When an acid (example HCl) is added to the solution .
CH3COO- + H+ ----------> CH3COOH
Acetate ion
The sodium acetate, is completely ionized. The CH 3COO- act as a “hydrogen ion sponge”. This
creates CH3COOH which does not dissociate extensively in water. Thus, the pH does not
change appreciably.
Control of pH in Body Fluids
Living systems are intricate chemical factories. They are desirable but delicate systems.
A myriad of chemical reactions are constantly taking place within them. Most of these reactions
produce organic acids which add protons as H + to the system which in turn will affect the pH of
the system. However, body pH should be maintained at a constant value. The importance of
pH control is illustrated in the case of human blood, in which pH must be kept within narrow
limits for life and even narrower limits for health, as illustrated in Fig. 2-3.
Blood pH Effect
8.2
8.1 Death from Tetany (Convulsion)
8.0
7.9
7.8
7.7 Alkalosis in Diseases( Nervous system is
7.6 affected , overexcited or extremely nervous)
7.5 Normal variation
7.4
7.3 Acidosis in Diseases ( Nervous system is affected,
7.2 depressed, person becomes disoriented
7.1
7.0
6.9 Death (Acidotic Coma)
6.8
6.7
6.5
Figure 2-3. Effect of pH changes in blood
Blood plasma has a normal pH of 7.4. If the pH should fall below 7.0 or rise above 7.8
the results would be fatal. Physiological pH is efficiently maintained by a buffer system. The
major buffer system in the blood is the carbonic acid-bicarbonate (H 2CO3-HCO3-) system
which is very effective in protecting this fluid from large changes in pH.
How does this buffer system protect the blood? Consider the following equilibrium
equation:
H2CO3 HCO3- + H+
Addition of a strong acid to blood will increase the H + and will consequently drive
the reaction to the left forming more carbonic acid. But carbonic acid is unstable and will
decompose to form carbon dioxide and water:
H2CO3 CO2 (g) + H2O
The carbon dioxide formed is removed from the blood and exhaled through the lungs.
The buffer is also effective when a strong base is added to blood. The mechanisms against both
acidosis and alkalosis are illustrated in Figure 2-4.
Figure 2-4. Action of H2CO3/HCO3- buffer system
Various factors can cause abnormal increase in acid or base levels in body fluids as
shown in Table 2-2.
Table 2-2 Acidosis and Alkalosis.
ACIDOSIS
Type Condition Results Causes Compensatory
from Reactions
Retention of CO2 Hypoventilation Increased rate of
breathing
Blood pH Emphysema Kidneys excrete
decreases acidic urine
Congestive heart
Respiratory failure
Bronchopneumonia
Hyaline membrane
disease
Drugs that depress
brain respiratory
center
Increase in H+ Diabetes mellitus Increased rate of
breathing
Blood pH Kidney failure Kidney excrete
Metabolic decreases acidic urine
Ingestion of acidic
drugs such as
aspirin
Loss of HCO3 -
ALKALOSIS
Type Condition Results Causes Compensatory
from Reactions
Rapid expulsion of Hyperventilation Slower rate of
CO2 breathing
Blood pH increases High fevers Kidneys excrete
Respiratory less acid
Trauma
Hysteria
Increase in alkaline Severe vomiting Slower rate of
components in the causing loss of breathing
blood stomach acid
Metabolic Blood pH increases Excess ingestion of Kidneys excrete
basic substances less acid
Kidney disease
Another effective buffer active mainly within the cells, hence called an intracellular
buffer, is the phosphate buffer system which has a maximum buffering capacity at pH 7.2.
H2PO4- ----------- HPO4- + H+
The action of the phosphate buffer is illustrated in Figure 2-5.
Figure 2-5. Action of the phosphate buffer
Normal biological reactions in living organisms result in the continuous production of
acids. The presence of buffer systems protects the organisms from changes in pH that would
otherwise be caused by these acids.
SUMMARY
Water is the most abundant compound in living organisms. Its unique properties make it
most suitable as the solvent of life. Mainly responsible for these properties are its polarity and H-
bonding capacity.
Acids are defined as proton donors and bases as proton acceptors. An acid/conjugate base
pair refers to a proton donor and its corresponding proton acceptor. Weak acids which display a
strong affinity for their protons are of great biological importance since they act as buffers to
resist changes in pH and therefore help to maintain normal internal pH in organisms.
In humans, the main extracellular buffering system is the carbonate-bicarbonate buffer
(H2CO3/HCO3- pair) and the principal intracellular system is the phosphate buffer, specifically
that which involves the second dissociation constant, Ka2 (H2PO4-/HPO4= pair).
KEY TERMS/CONCEPTS
Polarity
H-bonding
Universal solvent
Buffers
Buffering capacity
FLEXIBLE TEACHING LEARNING MODALITY (FTLM)
Module, Edmodo, Exercises
TEACHING AND LEARNING ACTIVTIES
MODULE 2. TEACHING AND LEARNING ACTIVTIES
Activity I.
Acidity, Basicity, Buffers and pH
Objective/s : 1. Define and describe acids and bases
2. Define and draw the pH scale
3. Define buffers and explain how they are related to biological systems
Instruction : Read the statements presented then answer the questions given.
A. Critical Reading: pH
When some substances dissolve in water they break up into ions. A compound that releases a
hydrogen ion (a proton) when it dissolves in water is an acid. Bases are compounds that accept hydrogen
ions. A solution’s acidity, or its hydrogen ion concentration, is measured on the pH scale. An acid has a
low pH (pH 0-7) and a high hydrogen ion concentration. A base has a high pH (pH 7-14) and a low
hydrogen ion concentration. Organisms must maintain a stable pH. Even a small change in pH can disrupt
many biological processes. Pure water has a neutral pH of 7.
1. What does an acid release when it is dissolved? ___________________________
2.. What does a base release when it is dissolved? ____________________________
3. What does a base accept? ______________________________
4. What is responsible for the acidity of a substance? ___________________________________
5. What does pH of a substance measure?________________________________
6. Draw the pH scale using numbers and label acid, neutral, and base. (Using numbers 0-14)
B. 1. A student mixes strawberry concentrate and water. A pH meter is used to measure pH of 5.4.
What kind of solution is the strawberry juice? _____________________
What is the ratio of the [OH-] and [ H+] present in the juice? _______________
2. A student adds an Alka-Seltzer to the strawberry juice prepared and stirs. The pH meter
now reads 8.3. What was released by the Alka-Seltzer tablet to cause this change? _______
Activity II.
Label each situation as an acid or a base.
Situation pH Acid or Base
a. Water directly out of faucet pH =7.2
b. pH after exhaled air is blown through a straw into pH=5.1
water for 5 min.
c. pH after a snail has lived in water for three days pH=5.8
d. pH of 2mL of bleach added with water pH=9.4
e. pH of instant coffee added with water pH=5.0
Activity III. Critical Reading: pH
A buffer is a mixture of molecules that releases or binds H+ in order to maintain a relatively
constant pH. Most buffers consist of a weak acid (which releases H+) and a weak base (which binds H+.)
Note that the function of a buffer is NOT to keep a solution neutral (at pH 7); its function is to minimize
the change in pH when base or acid is added to the solution. Buffers are extremely important to living
organisms because most biochemical processes proceed normally only when the pH remains within a
fairly narrow range. An excess of H+ or OH- can interfere with the structure and activity of many
biomolecules, especially proteins. Therefore, buffers are commonly used in living organisms to help
maintain a relatively stable pH. In humans, for example, buffers act to maintain blood pH between 7.35
and 7.45 even though acids and bases are continually being added to and removed from the blood as it
travels through the body. If the pH goes above the normal range, it is called alkalosis and if the pH goes
below the normal range it is known as acidosis.
1. Describe a buffer.
2. Why are buffers important to the human body?
3. List the symptoms of acidosis and alkalosis.
LEARNING MATERIALS AND RESOURCES
Videos
Transport in Cells: Diffusion and Osmosis
[Link]
Active transport : [Link]
Buffers in the blood [Link]
ASSESSMENT TASK
Quiz
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