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Body buffers and acid base

balance

Noor Ullah
M.Phil, Biochemistry& Mol.Biology
Lecturer IPMS, KMU

3/17/17 1
Ionization of water, weak acids and bases
Although many of the solvent properties of water can be explained
in terms of the uncharged H2O molecules, the small degree of
ionization of water molecules to hydrogen ions ions (H+) and
hydroxide ions (OH ) must also be taken into account.
Like all reversible reactions, the ionization of water can be
described by an equilibrium constant.
When weak acids or weak bases are dissolved in water, they can
contribute (H+ )by ionizing (if acids) or consume (H + )by
being protonated (if bases).
These processes are also governed by equilibrium constants.
The total hydrogen ion concentration from all sources,
which is experimentally measurable, is expressed as the
pH of the solution.
Ionization of water
Water molecules have a slight tendency to undergo
reversible ionization to yield a hydrogen ion and
a hydroxide ion.

This reversible ionization is crucial to the role of water


in cellular functions.
Equilibrium constant
The position of equilibrium of any chemical reaction is
given by its equilibrium constant. For the general
reaction,

An equilibrium constant can be defined in terms of


concentrations of reactants (A and B) and products (C
and D) present at equilibrium.
Equilibrium constant
The equilibrium constant is fixed and characteristic
for any given chemical reaction at a specific
temperature.

It defines the composition of the final equilibrium


mixture of that reaction, irrespective of the starting
amounts of reactants and products.
Equilibrium constant of water
As mentioned, the degree of ionization of water at
equilibrium is small.

At 25C, only about one of every (107 ) molecules in


pure water is ionized at any instant.

The equilibrium constant for the reversible ionization of


water is
Equilibrium constant of water
In pure water at 25C, the concentration of water is 55.5 M
(i.e., grams of H2O in 1 litre divided by gram
molecular weight or 1000/18 M = 55.5 M).
This value is essentially constant in relation to the very low
concentrations of (H+ )and (OH ) namely (1 107 )M.
Accordingly, on substituting 55.5 M in the equilibrium
constant expression we get

Which on rearrange become


Equilibrium constant of water
Where Kw designates the product (55.5 M) (Keq), the
ion product of water at 25C.

The value for Keq is (1.8 1016 )M at 25C as


calculated from electrical conductivity measurements.

Substituting this value for Keq in gives :


Equilibrium constant of water
Thus, the product [H+] [OH] in aqueous solutions at
25C always equals 1 1014 M2.
When there are exactly equal concentrations of both (H+
)and (OH ) as in pure water, the solution is said to be at
neutral pH.
At this pH, the concentration of (H+ )and (OH ) can be
calculated from the ion product of water as follows

Solving for [H+]


Equilibrium constant of water
As the ion product of water is constant, whenever
the concentration of H+ ions is greater than (1
107 )M, the concentration of (OH ) must become
less than 1 107 M, and vice versa.

When the concentration of (H+ )is very high, as in a


solution of hydrochloric acid, the (OH )concentration
must be very low.
pH and the pH scale
The ion product of water, Kw, is the basis for the pH scale.

It is a convenient means of designating the actual concentration of ( H+ )(and


thus of OH) in any aqueous solution in the range between (1.0 M H+ )and
(1.0 M OH ).

Biochemical reactions are often defined in terms of hydrogen ion (H+)


concentrations.

In 1909, Srensen, a Danish biochemist, used a logarithmic scale for


expressing the (H+ ) concentration. This scale was called pH, where p stands
for power and H for hydrogen ion concentration.

He defined pH of a solution as the negative logarithm of the


concentration (in moles/litre) of hydrogen ions. Thus,
pH and the pH scale
pH (short for potential of hydrogen) is a symbol
and denotes the relative concentration of
hydrogen ions in a solution.

pH values extend from O to 14; the lower the value,


the higher the acidity or the more hydrogen ions
the solution contains.

Water at 25 C has a concentration of H ion of 10-7; the


pH, therefore, is 7.
pH of water
The symbol p denotes negative logarithm of .
For a precisely neutral solution at 25C, in which the concentration of
hydrogen ions is 1.0 107 M, the pH can be calculated as follows :

To calculate the pH of a solution :


1. Calculate the hydrogen ion concentration, [H +].
2. Calculate the base 10 logarithm of [H +].
3. pH is the negative of the value found in step 2.
For example, for pure water at 25C :
pH = log [H+] = log 107 = ( 7) = 7.0
The pH scale
The pH scale was developed taking water as the standard.
It is an experimental fact that only 1 mole in 5,50,000,000 moles of water
ionizes into a H+ and OH.
This is the same proportion as 1 gram hydrogen ion in 10,000,000 litres of
water.
Hence, 1 litre of water contains 1/10,000,000 (or 1/107 = 107) of a gram of H+.
Later, for every day use, only the power figure was used and the symbol pH
placed before it.
A neutral solution, such as water, where the number of hydrogen ions is
balanced by the same number of hydroxyl ions, has a pH of 7.0.
The range of the pH scale is from 0 to 14. If the pH is 0, it would mean that 1
litre of water contained 1/1 = 1 gram hydrogen ion; or, at the other end
of the scale, if there were no hydrogen ion present, it would be written
1/1014 or 1014 or pH 14.
The pH scale, thus, runs from 1 to 14; neutrality being at pH 7.0.
Solutions having a pH lesser than 7 are acidic, conversely, solutions having a pH
more than 7 are basic or alkaline.
The pH scale
Note that the pH scale is logarithmic, not arithmetic.
Thus, when the pH of a solution decreases one unit from 5
to 4, the H+ concentration has increased tenfold from 105
to 104 M, since decimal logarithms are used for the pH
scale.
To say that two solutions differ in pH by 1 pH unit means
that one solution has ten times the H+ concentration of
the other.
A coca cola drink (pH 3.0) or red wine (pH 3.7) has an H+
concentration approximately 10,000 times greater than
that of blood (pH 7.4).
The pH scale
Body buffers
A buffer is a solution of a weak acid and its conjugate base that
resists changes in pH in both directionseither up or down.

A buffer works best in the middle of its range, where the amount of
undissociated acid is about equal to the amount of the conjugate
base.

One can soak up excess protons (acid), the other can soak up excess
hydroxide (base).
Blood Buffer Systems
Why necessary?

If the acids produced in the body from the catabolism of food


and other cellular processes are not removed or buffered, the
bodys pH would drop

Significant drops in pH interferes with cell enzyme systems.

pH control is important, as many enzymes have a narrow range


in which they function optimally.

Buffering capability is essential for the well-being of organisms,


to protect them from unwelcome changes in pH.
Acid-Base Balance
Normal pH of body fluids
Arterial blood is 7.4

Venous blood and interstitial fluid is 7.35

Intracellular fluid is 7.0

Alkalosis or alkalemia arterial blood pH rises above 7.45

Acidosis or acidemia arterial pH drops below 7.35


(physiological acidosis)
Sources of Hydrogen Ions
Most hydrogen ions originate from cellular metabolism

Breakdown of phosphorus-containing proteins releases


phosphoric acid into the extracellular fluid

Anaerobic respiration of glucose produces lactic acid

Fat metabolism yields organic acids and ketone bodies

Transporting carbon dioxide as bicarbonate releases hydrogen


ions
Regulation of body pH( H+)
Concentration of hydrogen ions(changes in blood pH) is regulated
sequentially by:

1. Chemical buffer systems act within seconds

2. Physiological buffer systems


The respiratory mechanisms hyperventilation or hypoventilation- acts
within 1-3 minutes

Renal mechanisms secretion of H + and reabsorption of HCO3 - - require


hours to days to effect pH changes
1. The chemical buffer system
Three major chemical buffer systems
Bicarbonate buffer system

Phosphate buffer system

Protein buffer system

Any drifts in pH are resisted by the entire chemical


buffering system
1. The chemical buffer system
1. Bicarbonate Buffer System: A mixture of carbonic acid
(H2CO3) and its salt, sodium bicarbonate (NaHCO3)
(potassium or magnesium bicarbonates work as well)
.If strong acid is added:
Hydrogen ions released combine with the bicarbonate ions and form
carbonic acid (a weak acid)
The pH of the solution decreases only slightly
.If strong base is added:
It reacts with the carbonic acid to form sodium bicarbonate (a weak
base)
The pH of the solution rises only slightly
.This system is the only important ECF buffer
1. The chemical buffer system
2. Phosphate buffer system: Almost identical to the
bicarbonate system. It is a mixture of Sodium salts of
dihydrogen phosphate (H2PO4), a weak acid and

Monohydrogen phosphate (HPO42), a weak base

This system is an effective buffer in urine and


intracellular fluid
1. The chemical buffer system
3. Protein buffer system:

Plasma and intracellular proteins(Albumin in blood plasma


and Hemoglobin in RBCs) are the bodys most abundant
and powerful buffers

Some amino acids of proteins have:


Free carboxyl group acts like an acid by releasing H +

Free amino group acts as a base to combine with H +

Amphoteric molecules are protein molecules that can


function as both a weak acid and a weak base
1. The chemical buffer system
3. Protein buffer system: Hemoglobin Buffer
System: Hemoglobin

Binds CO2

Binds and transports hydrogen and oxygen


Maintains blood pH as hemoglobin changes from
oxyhemoglobin to deoxyhemoglobin
2. Physiological buffer system
1. Respiratory mechanism- exhalation of carbon dioxide

.Increase in carbon dioxide in body fluids lowers pH of body fluids

.Because H2CO3 can be eliminated by exhaling CO2 it is called a volatile


acid

.Changes in the rate and depth of breathing can alter pH of body fluids
within minutes
Negative feedback loop
2. Physiological buffer system
2. Renal mechanism- Kidney excretion of H +

Metabolic reactions produce nonvolatile acids

One way to eliminate this huge load is to excrete H + in urine

In the proximal convoluted tubule, Na+/H+ antiporters secrete H+ as they reabsorb


Na+

Intercalated cells of collecting duct include proton pumps that secrete H + into

tubule fluid; reabsorb K+ and HCO3-

Urine can be up to 1000 times more acidic than blood

2 other buffers can combine with H + in collecting duct

HPO42- and NH3


Changes in blood pH
1. Respiratory acidosis

Abnormally high PCO2 in systemic arterial blood


Inadequate exhalation of CO2

Any condition that decreases movement of CO2 out emphysema,


pulmonary edema, airway obstruction
Kidneys can help raise blood pH

Goal to increase exhalation of CO2 ventilation therapy


Changes in blood pH
2. Respiratory alkalosis

Abnormally low PCO2 in systemic arterial blood


Cause is hyperventilation due to oxygen deficiency from high
altitude or pulmonary disease, stroke or severe anxiety
Renal compensation can help

One simple treatment to breather into paper bag for short


time
Changes in blood pH
3. Metabolic acidosis

Results from changes in HCO3- concentration


Metabolic acidosis abnormally low HCO3- in systemic arterial
blood
Loss of HCO3- from severe diarrhea or renal dysfunction

Accumulation of an acid other than carbonic acid ketosis

Failure of kidneys to excrete H+ from metabolism of dietary proteins

Hyperventilation can help

Administer IV sodium bicarbonate and correct cause of acidosis


Changes in blood pH
4. Metabolic alkalosis

Abnormally high HCO3- in systemic arterial blood


Non-respiratory loss of acid: vomiting of acidic stomach contents,
gastric suctioning
Excessive intake of alkaline drugs (antacids)

Use of certain diuretics

Severe dehydration

Hypoventilation can help

Give fluid solutions to correct Cl-, K+ and other electrolyte


deficiencies and correct cause of alkalosis
Henderson-Hasselbalch
Equation
The Henderson-Hasselbalch Equation is a
rearrangement of the Ka expression followed by the use
of negative logarithms. We will derive the HH equation
using the generic weak acid HA.

Here is the dissociation equation for HA:

HA H + A +
Henderson-Hasselbalch
Equation
On rearrangement we have the Ka expression:

Next, we isolate the H+ and put it on the left-hand side


of the equation:
Henderson-Hasselbalch
Equation
Now, taking the negative log of each of the three terms
in the above equation. We get:
-log [H+]= pH
- log Ka= pKa
-log ([HA] / [A])= + log ([A] / [HA])
Inserting these values, we get:
Henderson-Hasselbalch
Equation
Here is a common way the HH equation is presented in
a textbook explanation:
Henderson-Hasselbalch
Equation
However, remember that the salt of a weak acid is a
base (and the salt of a weak base is an acid).
Remember this: the base is the one WITHOUT the
proton and the acid is the one WITH the proton.
Here it is: