ACID-BASE EQUILIBRIA

CHEMICAL BUFFERS OF HUMAN BODY

ARRHENIUS ACIDS AND BASES

Arrhenius defined acids as substances that dissolve in water to release hydrogen ions (H+) into solution.

HCl H+(aq) + Cl- (aq)

Arrhenius defined bases as substances that dissolve in water to release hydroxide ions (OH-) into solution.

NaOH Na+(aq) + OH- (aq)

Brnsted-Lowry acids and bases

Brnsted-Lowry acids are donors of protons (H+) while bases are acceptors of protons.

HCl
donor-K1

H2O
acceptor-B2

H3O+(aq) + Cl- (aq)

donor-K2 + acceptor-B1 -

acceptor-B1

NH3 + H2O
+

donor-K2

donor-K1 NH4+(aq)

acceptor-B2

+ +

+OH- (aq) -

STRONG AND WEAK ACIDS

Strong acids completely (100%) dissociate in ions in water solution HCl + H2O HA + H2O H3O+ (aq) + Cl-(aq)
(100 % ions)

H 3O + +

A-

Weak acids dont dissociate completely and the equilibrium is moved toward undissociated acid. Concentrations of H3O+ and (A-) are low. CH3COOH + H2O CH3COO- + H3O+ HA + H2O H 3O + + AKeq = [H3O+][A-] [HA][H2O] Ka = Keq[H2O] = [H3O+][A-] [HA]

PURE WATER IS NEUTRAL!

Ionization of water gives the same concentrations of H+ and OH- ions.

H 2 O + H2 O

[H3O+] = 1,0 x 10-7 M [OH-] = 1,0 x 10-7 M

H3O + OHAcidic solution

Kw = [ H3O+][ OH- ] = 1,0 x 10-14

+ acid (H+)

+ base (OH-)

Basic solution

Comparison of [H3O+] and [OH-]

pH = - log [H3 O +] [H3O+] = 1 x 10-4 [H3O+] = 1 x 10-11 pH = 4.0 pH = 11.0

Acidic
0

Basic

1 2 3 4 5 6 7 8 9 10 11 12 13 14

Acidic, basic and neutral solution in our environment

pH values of body fluids and erythrocytes

Body fluids saliva gastric juice small intestine juice bile Pancreatic juice urine pH 5,06,8 1,02,0 7,08,0 5,88,5 8,08,3 4,87,8 Body fluids Vaginal secretion Amniotic fluid Blood plasma erythrocytes arterial blood pH

3,24,2 7,17,5 7,39 0,05 7,36 0,05 7,35 0,10

pH of Blood
pH of blood is 7,4, [H+] = 4 x 10-8 = 40 nmol H+ / L of blood Allowed variation of pH of blood is pH 0,05 or concentration of H+ 5 nmol / L blood

pH < 7,0 ARE INCOMPATIBLE WITH LIFE!

pH > 7,8
pH = 7,3 [H+] = 5 x 10-8 = 50 nmol H+ / L of blood Decreasing of pH for 0,1 unit, the concentration of [H+] increases for 25%. pH = 7,1 [H+] = 8 x 10-8 = 80 nmol H+ / L of blood Decreasing of pH for 0,3 unit, the concentration of [H+] increases twice.

CHEMICAL BUFFERS
Buffers are mixtures of weak acids and their conjugated
strong bases (salts) or mixtures of weak bases and their conjugated strong acids.

Chemical buffers confer resistance to a change in the pH of a solution when hydrogen ions (protons) or hydroxide ions are added or removed.

In comparison to buffers, when the acid or base is added to

the water, the pH value changes rapidly. Chemical buffers are important for normal function of bood cells. pH value of blood is 7.4. Change of pH of blood can cause disturbance in binding of oxygen and normal function of cell processes.

CHEMICAL BUFFERS
BUFFER: HA (weak acid)/A- (strong conjugated base)

NaA Na+ + A [H ][A ] [H ] K [HA] Ka a [A ] Henderson-Hasselbach [HA] HA H+ + Aequilibrium

[HA] - log[H ] logK a log [A ]

- If [HA] = [A-], then pH = pKa -pH of buffer does not change with dilution of solutions - Efficiency of buffer:
pH pKa log 10 pKa 1 1 pH pKa log

[A ] pH pK a log [HA]
1 pKa 1 10

pH = pKa 1

MECHANISM OF BUFFERS ACTION Buffer: HA/AHA H+ + A- NaA Na+ + A[A ] pH pK a log [HA]
HA + OH H2O + A

Henderson-Hasselbach equilibrium

Function of acidic component of buffer:

HA

A-

AHA

Function of basic component of buffer:

HA AHA A-

A-

H+

HA

SUMMARY OF BUFFER ACTION

Weak acid of buffer (HA) neutralizes added base. Conjugated base of buffer (A-) neutralizes added

acid. pH value of solution is kept unchangeable.

HA HA AAHA

A-

BLOOD BUFFERS
Blood buffers are:

Bicarbonate buffer, H2CO3 HCO3-, It is the most important inorganic blood buffer. It represents 5% of buffer systems in blood. Phosphate buffer, H2PO4- HPO42-; It represents 1% of buffer capacity of blood.
Proteins buffer, proteine proteinate, It represents 93% of buffer capacity of blood, 80% of it corresponds to hemoglobin and 13% corresponds to the rest of proteins of blood serum.

Bicarbonate buffer H2CO3 /HCO3The carbonic acid-hydrogen carbonate ion buffer works throughout the body to maintain the pH of blood plasma close to 7.40. The body maintains the buffer by eliminating either the acid (carbonic acid) or the base (hydrogen carbonate ions).

CO2(aq) + H2O(l)
CO2(aq) + H2O(l) CO2(g) CO2(aq)

H2CO3 (aq)

HCO3-(aq) +H+(aq)

HCO3-(aq) + H+(aq)

MECANISM OF ACTION:
HCO3-(aq) + H+ (aq) H2CO3(aq) + OH-(aq) H2CO3 (aq) H2O(l) + HCO3-(aq) CO2(aq) + H2O(l)

[CO2] = 0,03 x p CO2

Bicarbonate buffer

H2CO3 /HCO3-

Changes in carbonic acid concentration can be effected within seconds through increased or decreased respiration.

Changes in hydrogen carbonate ion concentration, however, require hours through the relatively slow elimination through the kidneys

ALKALOSIS AND ACIDOSIS

Blood pH can be disturbed by a number of respiratory and metabolic causes.

Respiratory Alkalosis
Respiratory alkalosis is a condition in which the pH of the blood is above
normal (pH > 7.4). The increase in pH value is often caused by hyperventilation (excessively deep breathing). When a person hyperventilates they exhale more carbon dioxide than normal. As a result the carbon dioxide concentration in the blood is reduced and the bicarbonate/carbonic acid equilibrium shifts to the left. The corresponding drop in H3O+ concentration causes an increase in pH.

2 H2O + CO2

H2CO3 + H2O

H3O+ + HCO3-

Respiratory alkalosis is treated by having the hyperventilating person

breathe into a paper bag. In doing so, they rebreathe some of expelled carbon dioxide, and blood carbon dioxide levels return to normal.

Respiratory Acidosis
Respiratory acidosis is caused by the reverse process (pH< 7.4). A hypo ventilating (excessively shallow breathing) person does not expel enough carbon dioxide and has elevated blood carbon dioxide levels. This causes the equilibrium to shift to the right, the H3O+ concentration increases and pH drops. 2 H2O + CO2 H2CO3 + H2O H3O+ + HCO3-

Metabolic Acidosis
Metabolic acidosis is a condition of low blood pH resulting from nonrespiratory causes. Those processes that remove bases from the body or produce acids may cause metabolic acidosis. A common example is overexertion. When a person overly exerts themselves an insufficient supply of oxygen to the active muscles results in the production of large amounts of lactic acid. If the amount of lactic acid produced exceeds the buffering capacity of the blood, the blood pH will be lowered.

Metabolic Alkalosis
Any condition in which a high blood pH is present due to non-respiratory
causes is called metabolic alkalosis. In general, those processes that remove acids from the body or produce bases may cause metabolic alkalosis. One example is the overuse of diuretics. Diuretics increase the amount of urine excreted from the body and, if the urine carries with it large amounts of acids, the blood pH will be increased.

Treatments of acidosis and alkalosis

Mild acidosis or alkalosis can often be treated by eliminating the root cause.
Considering our previous examples, this would simply mean reducing the amount of diuretics taken or forcing the person to rest.

In extreme cases, intravenous injections of weak acids or bases may be

performed. Bicarbonate (basic) solutions are used for patients experiencing extreme acidosis and ammonium chloride (acidic) solutions are used for those with extreme alkalosis.

PHOSPHATE BUFFER H2PO4- /HPO42(KH2PO4 i K2HPO4 in cells) (NaH2PO4 i Na2HPO4 in intercellular solutions) MECANISM OF ACTION: HPO42- + H+ H2PO4- + OHH2PO4H2O + HPO42-

Phosphate buffer takes place in homeostasis of HCO3- in kidneys H2PO4- + HCO3H2CO3 + HPO42H2O +CO2 CO2 (aq) + H2O
CA

HCO3- + H+

PHOSPHATE BUFFER H2PO4- /HPO42Phosphate buffer takes place in homeostasis of HCO3- in kidneys H2PO4- + HCO3H2CO3 + HPO42CO2 (aq) + H2O
CA

H2O +CO2
cells

HCO3- + H+

kidneys
H2PO4- + Na+

+ OHH2PO4+ H+
Blood circulation HPO42-

urine

HPO42- + 2Na+

Proteins buffer, proteine proteinate HPrPr-)

Groups of proteins which are donors and acceptors of protons: COOH + OH- COO- + H2O COO- + H+ COOH NH2 + H+ NH3+ NH3+ + OH- NH2 + H2O Basic groups confer resistance to change of concentration of H+ ions: Pr NH2 + H+ Pr NH3+ Pr - COO- + H+ Pr COOH

Acidic groups confer resistance to change of concentration of OH- ions:

Pr COOH + OH- Pr - COO- + H2O Pr NH3+ + OH- Pr NH2 + H2O

Pr COOH Pr COO- + H+; pH = pK(Pr COOH) + log [Pr COO-] / [Pr COOH];
Henderson-Hasselbach equilibria obtained from dissocitation of acidic proteins

Pr NH3+ Pr NH2 + H+ pH = pK (Pr NH3+) + log [Pr NH2] / [Pr NH3+]

NH3

Pr R

COOH

OH H
+

NH3

Pr R

COO-

OH H
+

NH2

Pr R

COO-

BLOOD GASSES
1. Blood rich in carbon dioxide is pumped from the heart into the lungs through the pulmonary arteries. (Arteries are blood vessels carrying blood away from the heart; veins are blood vessels carrying blood to the heart.) 2. In the lungs, CO2 in the blood is exchanged for O2. 3. The oxygen-rich blood is carried back to the heart through the pulmonary veins. 4. This oxygen-rich blood is then pumped from the heart to the many tissues and organs of the body, through the systemic arteries. 5. In the tissues, the arteries narrow to tiny capillaries. Here, O2 in the blood is exchanged for CO2. 6. The capillaries widen into the systemic veins, which carry the carbon-dioxide-rich blood back to the heart.

OXYGENATION (IN LUNGS)

HHb
in erythrocytes

from air

O2 HbO2-

H+
in erythrocytes

goes from erythrocytes to tissues

H+

Just formed

in erythrocytes removes by exhalation arrives from tissues ..............................................................................................................................

HCO3-

CO2

H2 O

HHb + O2 + HCO3- HbO2- + CO2 + H2O

DEOXIGANATION
In the presence of CO2 and H+ (e.g., in the muscles), charged groups are formed on the amino acid residues lining the subunit interface. These charged groups are held together by ionic interactions, forming "salt bridges" between the two subunits, and stabilizing the deoxygenated form of hemoglobin. When blood passes through the alveolar capillaries of the lungs, CO2 and H+ are removed from the hemoglobin, and the oxygenated configuration is favored (right).

DEOXIGANATION (IN TISSUES POOR IN OXYGEN)

CO2 +
from tissues

H2 O

in erythro. from tissues goes into the lungs

HCO3-

H+
in erythrocytes

H+

just formed arrives in tissues

in erythrocytes comes back to the lungs

HbO2-

HHb

in erythrocytes

goes to tissues poor in O2

O2

.............................................................................................................................. CO2 + H2O + HbO2- HHb + HCO3- + O2

CO2(aq)
In tissues

HHb(aq)

Hb-CO2(aq)

H+(aq)

just released by deoxigenation

carbamino-hemoglobin in erythrocytes