Water, PH and Buffers

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WATER, pH AND BUFFERS

Dr. Sehrish Lodhi


LEARNING OBJECTIVES
• Water , pH and buffers
a. Ionization of water, weak acids and bases.
b. pH and pH scale: Concept of pH and related topics ( determination of pH),
and concept of pl ( isoelectric pH)
c. pKa value, dissociation constant(Ka), and titration curve of weak acids
d. Determination of pH of buffer: Handerson- Hasselbalch equation and its
applications.
e. Body buffer systems and their mechanism of action.
WATER
• A DIPOLAR molecule
• Forms Hydrogen bond

• forms hydrogen bonds with other polar molecules and acts as a solvent
IONIZATION OF WATER
• H2O H+ + OH-
• Proton is highly hydrated

• H2O + H2O  H3O+ + OH-

• Protons exist in solution also as multimers such as H5O2+ and H7O3+

• Probability that a hydrogen exists as an ion is 0.01


Dissociation Constant of Water

• The ion product of water


ACIDS AND BASES
• Acids are proton donors and bases are proton acceptors.

• Strong acids completely dissociate into anions and protons even in


strongly acidic solutions (low pH).

• Similarly, strong bases are completely dissociated even at high pH.


• Weak acids dissociate only partially in acidic solutions.

• Similarly, weak bases like Ca(OH)2, do not completely dissociated at


high pH.
pH

• The concentration of H+ must be expressed in molar (M) terms


• A pH of 7 is termed neutral because [H+] and [OH-] are equal.
• Acidic solutions have a greater hydrogen ion concentration and a
lower hydroxide ion concentration than pure water (pH < 7.0)
• Basic solutions have a lower hydrogen ion concentration and a
greater hydroxide ion concentration (pH > 7.0).
Measurement of pH

• Measurements of the pH of blood and urine are commonly used in


medical diagnoses.

• The pH of the blood plasma of people with severe, uncontrolled


diabetes, for example, is often below the normal value of 7.4; this
condition is called acidosis.

• In certain other diseases the pH of the blood is higher than normal, a


condition known as alkalosis.
• Example 1: What is the pH of a solution whose hydrogen
ion concentration is 3.2 × 10-4 mol/L?

• Example 2: What is the pH of a solution whose hydroxide


ion concentration is 4.0 × 10-4 mol/L?
Hint : pH+ pOH = 14

• Example 3: What are the pH values of (a) 2.0 × 10-2 mol/L


KOH and of (b) 2.0 × 10-6 mol/L KOH? The OH- arises from
two sources, KOH and water.
DISSOCIATION CONSTANT OF ACIDS Ka
• The tendency of any acid (HA) to lose a proton and form its conjugate
base (A-)
pKa
• Since the numeric values of K a for weak acids are negative exponential numbers,
we express Ka as pKa, where:

• strong acid  high Ka  low pKa


weak acid  low Ka  high pKa

• It is the pH at which half of the protons is removed from the group OR


• The pKa of an acid group is the pH at which the protonated and unprotonated
species are present at equal concentrations.
TITRATION CURVE

• Titration is used to determine the amount of an acid in a


given solution.

• A plot of pH against the amount of OH added is called a


titration curve.

• It reveals the pKa of the weak acid.


BUFFERS
• Buffers are aqueous systems that tend to resist changes in pH
when small amounts of acid (H+) or base (OH–) are added.

• Buffers = weak acid [HA] + conjugate base [A-]

• A solution of a weak acid and its conjugate base buffers most


effectively in the pH range pKa ± 1.0 pH unit.
pKa depends upon:
1) Molecular structure:
2) Properties of the medium:
• The medium may either raise or lower the pKa relative to its value in
water, depending on whether the undissociated acid or its conjugate
base is the charged species.
• If ethanol is added to water, the pKa of a carboxylic acid increases,
whereas that of an amine decreases because ethanol decreases the
ability of water to solvate a charged species.
• The pKa values of dissociating groups in the interiors of proteins thus
are profoundly affected by their local environment, including the
presence or absence of water.
HENDERSON-HASSELBALCH EQUATION
• The relation between a weak acid (HA) and its conjugate base(A-) is
described by the HENDERSON-HASSELBALCH EQUATION

• When an acid is exactly half-neutralized, [A-] = [HA]:


• Calculate the fraction of histidine that has its imidazole side chain
protonated at pH 7.3. The pKa values for histidine are pK1 = 1.8, pK2
(imidazole) = 6.0, and pK3 = 9.2
Applications of the Henderson-Hasselbalch Equation
Drug Absorbtion
• Acidic drugs: HA A- + H+
• Basic drugs ; BH+ B + H+
• A drug passes through membranes
more readily if it is uncharged.
• Thus, for a weak acid, such as aspirin,
the uncharged HA can permeate
through membranes, but A– cannot.
• For a weak base, such as morphine,
the uncharged form, B, penetrates
through the cell membrane, but BH+
does not.
• Therefore, the effective concentration of the permeable form of each
drug at its absorption site is determined by the relative concentrations
of the charged (impermeant) and uncharged (permeant) forms.

• The ratio between the two forms is determined by the pH at the site of
absorption, and by the pKa of the ionizable group.

• The Henderson-Hasselbalch equation is useful in determining how


much drug is found on either side of a membrane that separates two
compartments that differ in pH, for example, the stomach (ph 1.0–1.5)
and blood plasma (ph 7.4).

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