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    22BM402 LM2

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    22BM402 LM2

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    22BM402 LM2

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    22BM402 – BIOSCIENCES IN MEDICAL ENGINEERING

    UNIT 1 & LP2- Handerson- Hasselbalch equation, physiological


    buffers
    1. HANDERSON- HASSELBALCH EQUATION
    The Henderson-Hasselbalch equation provides a relationship between the pH of acids (in
    aqueous solutions) and their pKa (acid dissociation constant). The pH of a buffer solution can
    be estimated with the help of this equation when the concentration of the acid and its conjugate
    base, or the base and the corresponding conjugate acid, are known.
    Equation of Henderson-Hasselbalch
    The Henderson-Hasselbalch equation can be written as:
    pH = pKa + log10 ([A–]/[HA])
    Where [A–] denotes the molar concentration of the conjugate base (of the acid) and [HA]
    denotes the molar concentration of the weak acid. Therefore, the Henderson-Hasselbalch
    equation can also be written as:

    An equation that could calculate the pH value of a given buffer solution was first derived by
    the American chemist Lawrence Joseph Henderson. This equation was then re-expressed in
    logarithmic terms by the Danish chemist Karl Albert Hasselbalch. The resulting equation was
    named the Henderson-Hasselbalch Equation.

    1.1 Derivation of the Henderson-Hasselbalch Equation


    The ionization constants of strong acids and strong bases can be easily calculated with the help
    of direct methods. However, the same methods cannot be used with weak acids and bases since
    the extent of ionization of these acids and bases is very low (weak acids and bases hardly
    ionize). Therefore, in order to approximate the pH of these types of solutions, the Henderson-
    Hasselbalch Equation is used.
    The above equation is known as Henderson-Hasselbalch equation, popularly known as
    Henderson equation. It is very useful for estimating the pH of a buffer solution and finding the
    equilibrium pH in acid-base reactions. From the equation, we can infer when
    When exactly half of the acid undergoes dissociation, the value of [A]/[HA] becomes 1,
    implying that the pKa of the acid is equal to the pH of the solution at this point. (pH = pKa +
    log10(1) = pKa).
    For every unit change in the pH to pKa ratio, a tenfold change occurs in the ratio of the
    associated acid to the dissociated acid. For example, when the pKa of the acid is 7 and the pH
    of the solution is 6, the value of [A–]/[HA] is 0.1 but when the pH of the solution becomes 5,
    the value of [A–]/[HA] becomes 0.01.
    The value of [A–]/[HA] is dependent on the value of the pH and pKa. When pH < pKa; [A–
    ]/[HA] < 1. When pH > pKa; [A–]/[HA] > 1.

    1.2 Limitations of the Henderson-Hasselbalch Equation


    The Henderson-Hasselbalch equation fails to predict accurate values for the strong acids and
    strong bases because it assumes that the concentration of the acid and its conjugate base at
    chemical equilibrium will remain the same as the formal concentration (the binding of protons
    to the base is neglected).
    Since the Henderson-Hasselbalch equation does not consider the self-dissociation undergone
    by water, it fails to offer accurate pH values for extremely dilute buffer solutions.
    Problem : A buffer solution is made from 0.4M CH3COOH and 0.6M CH3COO–. If the acid
    dissociation constant of CH3COOH is 1.8*10-5, what is the pH of the buffer solution?
    As per the Henderson-Hasselbalch equation, pH = pKa + log([CH3COO–]/[CH3COOH])

    Here, Ka = 1.8*10-5 ⇒ pKa= -log(1.8*10-5) = 4.7 (approx.).

    Substituting the values, we get:


    pH = 4.7 + log(0.6M /0.4M) = 4.7 + log(1.5) = 4.7 + 0.17 = 4.87
    Therefore, the pH of the solution is 4.87.

    2. BUFFER
    A buffer is an aqueous solution consisting of a mixture of a weak acid and its salt (acidic buffer)
    or a weak base and its salt (basic buffer) that resists a change in pH on the addition of either
    acid or base.Its pH changes very little when a small amount of strong acid or base is added to
    it and thus it is used to prevent changes in the pH of a solution.
    In practice, a buffer solution consists of an aqueous mixture of a weak acid and its conjugate
    base. The conjugate base component would neutralise any hydrogen ions generated during an
    experiment whilst the unionised acid would neutralise any base generated.

    2.1 Physiological Buffers

    Although the lung's ability to expel CO2 and the kidney’s ability to excrete or absorb hydrogen
    ions allow close regulation of pH, their responses alone are not sufficient to prevent immediate
    local changes in pH at the tissue. This is the role of the buffering systems.

    Buffering systems are chemicals within tissue and the blood that have the ability to absorb
    either hydrogen ions and/or hydroxyl ions. Once these ions are removed from solution (albeit
    temporarily) then their effect on pH is diminished. We will deal with buffers in the context of
    acids, as this is the most common physiological situation.

    If you need an analogy for the function of buffers, imagine them as a chemical mop—they soak
    up the hydrogen ions and stop them from making a cellular mess, but the hydrogen ions,
    although contained, remain in the system. It is the role of the lungs and kidneys to "rinse the
    mop" and get rid of the hydrogen ions from the system.

    There are three major chemical buffering groups in the body:


    1. the bicarbonate system,
    2. the phosphate system, and
    3. intra- and extracellular proteins.

    We will deal with the bicarbonate system as it involves the respiratory system and is also the
    major extracellular buffer.

    Bicarbonate buffering: A buffering system consists of a weak base capable of absorbing a


    strong acid and a weak acid capable of absorbing a strong base. As such, the bicarbonate system
    involves two components: sodium bicarbonate (a weak base) and carbonic acid (a weak acid).
    Let us look at how it works and put it in the context of the lungs.

    First let us see how a weak acid (carbonic acid) deals with a strong base, in this example,
    sodium hydroxide (equation 1).

    Buffering a strong base using a weak acid:

    NaOH=H2CO3 (1)

    Sodium hydroxide is a strong base as it rapidly dissociates into a hydroxyl ion and a sodium
    ion.

    Na+OH−+H2CO3 (2)

    The hydroxyl ion is the potential threat to physiological function so must be buffered. This is
    achieved by the carbonic acid dissociating into a hydrogen ion and bicarbonate (a process you
    are familiar with).

    These dissociated ions now bind to form new partnerships as water and sodium hydroxide (a
    weak base) (equation 3).

    Na+OH−+HCO3−H+⇒H2O+NaHCO3 (3)

    So there are a couple of things to notice here beyond watching the ions move and form new
    components. First, the buffering process has taken a situation with the threat from a strong base
    (NaOH) and toned it down to a situation with a weak base (NaHCO3); the problem has not
    gone away, it has just been reduced (or buffered). Second, you will see that both of the
    components of the bicarbonate system, carbonic acid and sodium bicarbonate, appear in the
    equation—we have just shifted from one to the other.

    Let us look at the opposite situation to see what happens when the buffering system is faced
    with a strong acid. This time a strong acid (hydrochloric acid) is faced with our weak base
    (sodium bicarbonate) (equation 4).
    Buffering a strong acid using a weak base:

    HCl+NaHCO3 (4)

    The hydrochloric acid rapidly dissociates into a hydrogen ion and a chloride ion. The hydrogen
    ion now threatens physiological function and must be buffered.

    Our weak base dissociates into sodium and bicarbonate ions. Again our ions recombine, this
    time to produce harmless sodium chloride and carbonic acid (equation 5).

    H+Cl−+HCO3−Na+⇒NaCl+H2CO3 (5)

    Notice again we have reduced but not removed the threat as we have gone from the presence
    of a strong acid to a weak one. Also notice that our two components in the bicarbonate system
    appear in the equation, and we have switched from one to the other. This should now make you
    realize that these two components are part of a reversible equation, and this reversible equation,
    even after the addition of sodium to one end, should look rather familiar (equation 6).

    CO2+H2O↔H2CO3↔H++HCO3−+Na+↔NaHCO3 (6)
    Alveolar ventilation can influence the bicarbonate buffering system.Because of their critical
    role in maintaining blood pH, bicarbonate ions are routinely measured along with arterial blood
    gases. Knowing what the blood pH, arterial CO2, and bicarbonate levels are provides a very
    powerful and commonly used diagnostic measure allowing us not only to determine the pH
    status of the patient, but also the source of the problem and whether the renal or pulmonary
    systems are achieving compensation.

    Chemicals used by the body to prevent large changes in the pH of a bodily fluid
    1. Carbonic acid–bicarbonate buffer system: – most important in ECF
    2. Phosphate buffer system: – buffers pH of ICF and urine
    3. Protein buffer systems: – help regulate pH in ECF and ICF.

    Carbonic acid–bicarbonate buffer system


    Overall Reaction

    CO2 + H2O ⇔ H+ + HCO3


    Removing CO2 from the blood-increase the pH. Removing HCO3- from the blood -lower the
    pH.
    If you add base to blood, it will be neutralized by the reaction

    H2CO3 + OH- ⇔ HCO3- + H2O


    If you add acid to blood, it will be neutralized by the reaction

    HCO3- + H+ ⇔ H2CO3
    Phosphate Buffer
    The phosphate buffer system consists of H2PO4− and HPO4
    The equilibrium is

    H2PO4−(aq) + H2O ⇌ H3O+(aq) + HPO42− (aq); pKa = 7.21

    The phosphate buffer can easily maintain a pH of 7.4.


    3. Protein buffer
    A protein is a long chain of amino acid residues, but this long chain still has free carboxylate
    groups COO− and free amino groups NH2
    Equation for a protein buffer system as

    H3+N-R-COO− + H2O ⇌ H2N-R-COO− + H3O+

    The protein can then act as a buffer.

    3 FITNESS OF THE AQUEOUS ENVIRONMENT FOR LIVING


    ORGANISM
    Water is the best option for the aqueous environment for living organism.

    • Water : The molecule that support all of life


    • Water is a biological medium on earth
    • All living organism require water
    • Cells are about 70-95% water
    • Water is the main reason for the earth is habitable
    Cohesive behavior: Attraction of water molecules each other due to H bonding. The positive
    side on one water molecule comes near the negative side of another water molecule, they attract
    each other and form a bond. This "bipolar" nature of water molecules gives water its cohesive
    nature. Water is sticky and clumps together into drops because of its cohesive properties

    Ability to moderate temperature: water has high specific heat: Can absorb/release a large
    amount of heat to/from the air with only slight change in the temperature: Also has high heat
    of vaporization : helps the temperature stabilization in organisms.
    Ability to moderate temperature: water has high specific heat: Can absorb/release a large
    amount of heat to/from the air with only slight change in the temperature: Also has high heat
    of vaporization : helps the temperature stabilization in organisms.

    Versatility as a solvent Due to its polarity


    When an ionic compound dissolved in a water, each ions will be surrounded by a sphere of
    water molecules , a hydration shell
    Water can dissolve compounds made of non-ionic polar molecules Even large polar molecules
    such as proteins can dissolve in water if they have ionic and polar regions.

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