Chemical Kinetics Water Water Chemical Kinetics Water Water

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CHEMICAL KINETICS

WATER

LECTURE 3
CHEMICAL KINETICS
Chemical thermodynamics :
• It studies the energy variation of chemical systems during their
transformations.
• It foresees the sense a system is spontaneously transformed,
from the initial state to the equilibrium state.
• it does not give indications about the time needed to attend
the equilibrium state, does not say about the reaction velocity
and does not indicate the nature of reactant transformations.
transformations
• It will not even help to anticipate if a “thermodynamically
possible” reaction will take place or not.
• With enough certitude it will permit to affirm that a
“thermodynamically impossible” reaction will not take place
spontaneously!
• Chemical kinetic measures the reaction velocity
• The velocity of a chemical reaction can be influenced by
medium factors as temperature and pressure, particles
dimensions, the presence of a catalyst or even the recipient
form.
• In many reactions, the obtained products are not the most
stable ones, but others, less stable but with a life long enough
to participate to secondary chemical reactions.
• The system, also, is not the most stable one. A high number of
chemical substances are found, in normal conditions, in a
thermodynamic instability.
• In many cases, intermediary compounds appear, unstable
chemical species with a very short lifetime.
• reaction mechanism - allll the knowledge about the
intermediary steps a system follows in a chemical
transformation
• reaction velocity, v, - the reactant quantity consumed per unit
of time, respectively the product quantity formed per unit of
time.
• For a reaction A → B, the velocity is defined as:

∆[A] [A]final − [A]initial ∆B


v=− =− =
∆t [ t ]final − [ t ]initial ∆t

• Practically, the determination of average reaction velocity can


be done by measuring the reactant/product quantity that
modifies during the reaction.
• If Δt tends to 0, then the instantaneous velocity or reaction
rate (velocity) is obtained.
Reaction order
• Considering a homogenous chemical process in gaseous state at constant
temperature:
n1R1 + n2R2 → products
• the reaction velocity is expressed as the disappearing velocity of reactants
R1 or R2:
v = k[R1]a[R2]b
• with k – rate constant,, defined as being equal to the process rate when the
reactant concentrations are equal to unit;
• a and b represent the partial reaction orders as function of reactants R1 and
R2.
• The partial reaction orders can be equal or different comparing to the
stoechiometric coefficients n1 and n2. Reaction order is defined as the sum
of partial reaction orders:
n=a+b
• Reaction order has no relations with reaction molecularity,
molecularity but can be
equal to that one in the simple reaction case.
case
• chemical reactions are divided into reaction of zero, first, second, tertiary,
and so on, order
Zero order reactions (n=0);
• reaction rate is independent of concentration.
• Examples of zero order reactions are radioactive
decompositions. The rate of these reactions does not
depend on the radioactive element concentration and is
constant till last atom is decomposed.
v=k
First order reactions (n=1),
• Generally, these reactions correspond to one of the
variants:
A → B, A → B + C, A + B→ C + D.
• Reaction rate depends on the reactant concentration at
power 1:
v = k[A]
Second order reactions (n=2);
• rate is proportional to square concentration
• For a process like:
2A → products
• the rate of the second order reaction is:
v = k[A]2
• and for a reaction as:
A + B → products
• the rate is:
v = k[A][B]

The half time is defined as the time needed to consume half of


the reactant quantity.
CATALYSIS
• The number of collisions of gas molecules per unit of time is
extremely high.
• Molecules in a moll of gas, at 0°CC and 1 atm, suffer a number of
31
approx. 10 collisions per second with other molecules.
• If each bimolecular collision would be efficient, the reaction should
take place in an incredible short time of around 10-9 seconds.
• the majority of collisions are not efficient, therefore do not conduct
to chemical reactions. Only a small fraction of gas molecules
effectively react, we say they are activated.
• reaction velocity increases as temperature increases,
increases and the kinetic
energy increases with temperature increasing
• ⇒ activation = increase of kinetic energy of molecules.
molecules
• It is plausible that only molecules having a higher kinetic energy than
a certain threshold (E) react.
Activation energy:
• A catalyst is a compound that, being
present, increases the reaction rate.
• The catalyst is found unchanged at the
end of the reaction, qualitatively and
quantitatively.
• Catalyst determines or accelerates only
the thermodynamically possible reactions
that mean reactions, which take place
spontaneously with the increase of the
free enthalpy of the reaction.
• A catalyst cannot displace the chemical
equilibrium that means it cannot modify
the equilibrium constant, Ke. Such a
change would imply creation or
https://www.chemicool.com/definition/catalyst.html destruction of energy.

Catalysts influence the kinetic and mechanism of reactions,


but without influencing the equilibrium.
• Different catalysts,, acting on the same substrate may give rise
to different reaction products.. Example: Ethanol can be
transformed at 3000C in ethene or acetaldehyde:

CH3CH2OH   → CH =CH + H O
Al2O3
2 2 2

→
Cu

CH3CH2OH CH3CH=O + H2

• Enzymes are organic catalysts, produced and used in the living


cells for the biochemical reactions. Enzymes have a substrate
specificity that means they do not catalyze but the reaction in
which a certain reactant participates, some time a certain
molecular form of that one (a certain isomer).
CHEMICAL EQUILIBRIUM

• A chemical reaction that takes place in a closed recipient (to avoid the material
changes with the exterior) implies modifications in the masses of the components of
the system: some components are consumed and others are produced.
• After a variable period of time any mass modification of the system components will
cease as long as the system is not disturbed.
disturbed In that situation, one can talk about the
equilibrium state of the system. Practically, the chemical processes never end, only
that, at one moment, the rate with which one compound is formed equals the rate
with which that compound decomposes, and, practically, the system composition
does not change after the equilibrium is installed.
• Only an external factor can change that equilibrium
• It is said that a chemical reaction is at equilibrium as long as there is no any
tendency of modification of reactant and product quantities.
A B

• If the Equilibrium State implies the existence of significant quantities of both,


products and reactants, then the reaction is incomplete or reversible.
• If one of the factors, which determine the chemical
equilibrium, is modified, the equilibrium will move to that
direction in which the modification of that factor is
diminished. That is in fact the principle of Le Chatelier,
which also says:
• The increasing of one of the components of a mixture, found
at equilibrium, will turn the equilibrium in the sense of
consuming of that component.
• The increasing of temperature will turn the equilibrium in
that direction in which the concentration of components,
which formation consumes energy, will increase.
• The increasing of pressure will turn the equilibrium in that
direction in which components with a smaller volume are
formed.
Mass Action Low
• the equilibrium state can be treated from both directions. A
reaction like the following one:
aA + bB ⇔ cC + dD
• is, in fact, a competition between the forward reaction and the
reverse one.
• At equilibrium, the rates for both reactions are equal,
therefore no macroscopic modification can be seen, even if the
transformations continue at the microscopic level.
Vforward r. = k1[A]a[B]b
Vreverse r. = k2[C]c[D]d
• In time, the forward reaction rate decreases and the reverse
one increases;
• at equilibrium, the two reaction rate become equal:

Vforward r. = Vreverse r. and k1[A]a[B]b = k2[C]c[D]d


• If in that moment, an intervention in the system is done,
and a C quantity is added or a A quantity is removed (so the
active masses are modified), the reverse reaction rate will
be higher than the forward one and a new modification on
the mixture composition will be appear, in the aim of
touching of a new equilibrium state.
• At constant temperature, the ratio of the product
concentrations and reactant concentrations is constant.
That ratio is noted with K, which is denominated the
equilibrium constant:

K=
[C] [D]
c d

[A ] [B]
a b
• The ∆GG values can be used for the determination of the equilibrium
constant, noted with K. The calculation of total free energy includes the
free energies of reactants and products:
products
∆G = Gproducts – Greactants
• This mathematic relation includes the molar partial free energies, therefore
the relation becomes:
∆G = ∆G° + RTln{[C][D]/[A][B]}
For a reaction as:
A+B↔C+D
• When this equation is used for an equilibrium reaction, the concentrations
of the species A, B, C, D will be equilibrium concentrations,
concentrations and the ratio of
the concentrations of products and reagents will equal K.
• Also, at equilibrium, ∆GG = 0 and therefore:
0 = ∆G° + RTlnK
∆ = -RTlnK
∆G°
WATER, H2O

• it covers more than 2/3 of Terra’ surface, forming the surface water.
• Atmosphere contains water vapors in different concentrations.
• Water derived from vapor condensation is called meteoric water, and it arrives
again on earth, in surface waters, or it can penetrate through the permeable ground
layers until it arrives to an impermeable layer, forming a layer of ground water.
• Chemical composition of these spring waters varies as a function of the nature of
rocks they were in contact with. Spring water contains dissolved air gases (oxygen,
nitrogen, carbon dioxide), cations (calcium, magnesium, sodium) and anions
(bicarbonate, sulfate and chloride).
Water is a compulsory constituent of the living world, which permits the proceeding
of the following processes:
• All the substances, needed for the existence of the living world, are found
dissolved in water solutions in the surrounding medium.
• All the reactants and products of the metabolic reactions, nutrients and residual
products depend on water to be transported intracellular or extracellular.
• All the structures of the main biomolecules (proteins, nucleic acids, membrane
lipids, etc) result only as a consequence of the interaction with the aqueous
medium.
As for the human organism, this one contains, function of age and adiposity, 58 -
66% water, from which 40 - 45% in the intracellular compartment and the rest
extracellular, the two compartments being separated by cell membranes.
Water is found as water solutions, which composition differs as a function of the
cell type or the extracellular fluid.
Constancy maintaining of water quantity in the organism enforces a daily intake of
water, otherwise the organism dies in a short time.
PHYSICAL PROPERTIES
Water is a liquid, colorless in small quantities
Water physical Values
(watched in thick layer, it has a greenish-blue
blue characteristics
color), tasteless, and odourless. Melting point, oC 0oC

Water has maximal density at 4oC (ρ== 1 g/cm3). Boiling point , oC 100oC

Water has melting and boiling points higher than Density, g/cm3 at 0oC – solid
- liquid
0.91608
0.999868
other hydrides of elements in the oxygen group o
at 4 C 1.000000
at 20oC 0.998230
(H2S, H2Se, H2Te).
Specific heat at 15oC, J/g 4.18
Due to its high specific heat, water can receive or Melting heat, kJ/mol 6.0
give a considerable quantity of heat, without
modifying considerably its own temperature. Vaporization heat, kJ/mol 40.7

Dielectric constant at 25oC 78.54


Pure water has very low electric conductivity due
to its extremely low ionization (ionic product of Electric moment, Debye 1.85

water is 1.1 x 10-14 iongram/l, at 20oC). Conductivity la 18oC, Ω-1· 4· 10-8


cm-1
Instead, its dielectric constant is high, which
explains its property of solving the ionic or polar
covalent substances.
• These unusual properties are a consequence of attractions
between adjacent water molecules that give a great internal
cohesion to liquid water.
• A look at the electron structure of the H2O molecule reveals
the cause of these intermolecular attractions.
• Each hydrogen atom of a water molecule shares an electron
pair with the central oxygen atom.
• The geometry of the molecule is dictated by the shapes of the
outer electron orbitals of the oxygen atom, which are similar to
the sp3 bonding orbitals of carbon. These orbitals describe a
rough tetrahedron, with a hydrogen atom at each of two
corners and unshared electron pairs at the other two corners
ice melted ice water
Water chemical properties
1. Oxidation-reduction
reduction character
• Water can react as follows:
2H2O + 2e- → H2 + 2HO- E0= - 0,83V (oxid. character)
2H2O - 4e- → O2 + 4H+ E0= - 1,23V (red. character)
• Reducing agents stronger than hydrogen (alkaline metals, metals
from second group, Fe) reduce water, liberating hydrogen.
• Strong oxidizing agents with normal potentials higher than 0.83 V,
as: fluorine - at high temperatures, chlorine and silver at light
oxidize water, liberating oxygen.
2. Water reactions with acid and basic oxides form the
corresponding oxoacids or hydroxyls. Examples:
CaO + H2O → Ca(OH)2
SO2 + H2O → H2SO3
3. Water as a ligand
• Water can function as a ligand in the formation of complex
combinations, called aqua-complexes
complexes or hydrates, due to its
polar character and the presence of 2 lone pairs of electrons at
the oxygen atom.
• Ex. [Al(H2O)6]Cl3, Na2CO3·10H2O, CuSO4·5H2O, [Mg(H2O)6]Cl2.
• Interactions of water molecules with the ion, which generates
the complex, are coordinative bonds (donor – acceptor type),
or ion – dipole type.
• Some time, hydrating water is eliminated when solutions are
evaporated, some time water is part of the dissolved crystals,
as whole molecules, forming crystallizing water: (Na2CO3·10
H2O, MgCl2·6H2O, FeSO4·7H2O).
ACIDO – BASIC CHARACTER
Acid - in an ionolytic solvent (that dissociate in ions), is any dissolved substance,
more or less dissociated in ions, and whose positive ion is identical with the one
that results from the solvent dissociation.
dissociation
• In water, all the substances that dissociate hydrogen ions (hydronium) will be
acids.
• In liquid ammonia, where the ions: NH4+ and NH2- exist, all the ammonium salts
will be acids.
• The ionization reaction of any acid can be represented as:

-
HA H ++ A
• The equilibrium constant for this system is: Ka acidity constant

[ H + ][ A − ]
Ka =
[ HA]
• As a function of this constant acids can be strong or weak. The strong acids are
totally ionized, and the weak one are partially ionizes and have an acidity
constant lower than 1
Base - in an ionolytic solvent, is any dissolved substance, more or less
dissociated in ions and whose negative ion is identical with the one that
results from the solvent dissociation.. In water, all the substances that
dissociate hydroxyl ions will be bases.
• A series of bases have ionic character even in the crystallized form, so they
are totally dissociated in solution. This is the category of the strong bases.
There are other bases that dissociate partially, as the following equilibrium:

-
BOH B ++ HO

• The equilibrium constant in this case is: Kb basicity constant


[ B + ][ HO − ]
Kb =
[ BOH ]

• The product formed by the ionization of an acid represents is conjugated


base.
• Reversely the protonation of a base gives rise to its conjugated acid. Acetic
acid and the acetate ion, for example, form a conjugated pair acid-base:
acid
CH3COOH + H2O CH3COO- + H3O +
Water ionization
• Water is an amphoteric substance, functioning both as a proton donor (acid)
and an acceptor (base). Its dissociation gives rise to hydronium ions (H3O+) and
hydroxyl ones (HO-):

2H2O H3O+ + HO-

• To simplify, we will refer for the hydronium ion as being hydrogen ion (H+) and
we can write the equilibrium as follows:
-
H2O H ++ HO

• The equilibrium constant, Ke, 0f this reaction will be:


Ke =
[H + ][HO − ] (1)
[H 2O]
• Because the concentration of pure water (water concentration in water is 55.5
M) is very little changed by ionization, the concentration in water molecule is
practically constant and is included in the equilibrium constant, and the
expression (1) can be simplified as:
PH2O = KH2O = [H+] [HO-] (2)
KH2O (PH2O) = ionic product of water
At 25°C, KH2O is 1 · 10-14 mol2/l2
pH definition
• pH is a measure of the concentration in hydrogen ions of a solution.
• It is defined as the negative decimal logarithm of the hydrogen ions
concentration
1
pH = log + = − log H +
[ ] [ ]
H
• Henderson - Hasselbalch equation – Dissociation constant

Ka =
+ −
[ H ][ A ⇒
] + [A ]
= log[H ] + log ⇒

− log [H +
] = −logK + log
[A ]

[ HA]
[HA
log K e
[HA] [HA ]
• If pH is noted as pH = - log [H+] and pK = - log K, then:

pH = pK + log
[ A ]−

[ HA] Henderson
Henderson-Hasselbalch equation
• The arrangement of the pH values from pH 0 ([H+] = 1) to pH 14 ([HO-] = 1) permits to obtain a pH
scale used in practice to give the hydrogen ion concentration of solutions.
• The pH scale contains:
• a zone with excess of H+ - the acid zone (pH 0 - 7),
• a point at which H+ = HO- - the neutrality point (pH = 7) and
• a zone with excess of HO- - the alkaline zone (pH 7 - 14).

• Between the concentrations of hydrogen and hydroxyl ions, on one side, and the corresponding
upper indexes, on the other hand, there are well defined relations, which can be resumed in the
following table:

[H3O+] 1 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14

[HO-] 10-14 10-13 10-12 10-11 10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 1

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pOH 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0

Acid solution Netral Alkaline solution


• In biochemistry the dissociation reaction, in which protons
participate, all the time the sense of reaction is considered to
be the sense of proton releasing:
H2CO3 HCO3 + H+
NH4 NH + H+
3

HPO4 + H+
2
H2PO4

• Therefore, the dissociation constant is all the time the acidity


constant (Ka) and pK is pKa
• If the molecules present more then a dissociable proton, pK
values are counted in the order of pH increasing. For H3PO4:

pK1
H3PO4 H2PO4 + H+
pK2
HPO4 + H+
2
H2PO4
pK3 3-
PO4 + H+
2
HPO4
• From the Henderson - Hasselbalch equation it can be observed that pK is, in fact, a
pH value – that pH at which the concentrations of the dissociated and non-
non
dissociated forms are equal.

pH = pK + log
[A ] −
[A–] = [HA] ⇒ pK = pH
[ HA]
Calculation of pH for acid, base and salt solutions
a. Strong acid and strong base solutions
• totally dissociated,
• the hydrogen ions concentration will be equal with the equivalent
concentration of the acid or base. In this case:
[H+] = [HA] şi [HO–] = [BOH]
• And so for the strong acid solutions:
pH = - log[HA]
• and for strong base solutions:
pOH = - log[BOH] and pH = 14 – pOH
b. Weak acid and base solutions.
• In the solutions of weak acids, partially dissociated,
dissociated the hydrogen ion
concentration is calculated starting from the acidity constant, Ka:
HA H+ + A-
Ka =
[ ][ ]
H + A−
[ HA]
• If we note with c the initial concentration of the acid, it results:
[HA] = c – [H+], and as [A-] = [H+],, we can write:

[ H ]+ 2

Ka =
c − [H ] +

• From where: [H+]2 + Ka[H+] - Kac = 0


• Or

+
Ka K a2
[H ] = − + + Kac
2 4

• For the very weak acids ⇒ [H + ] = orK a c [ HO − ] = Kbc


Calculation of pH for salt solution. Hydrolysis
• If, by the dissolving in water of a salt, an anion of a partially dissociated acid
results, then the following reaction takes place (a reaction with hydrogen
ion formed in the water dissociation):
A- + H+ + HO- HA + HO-
• If the salt cation is one of a base partially dissociated, then the following
reaction will take place with the resulted hydroxyl ion from the water
dissociation:
B+ + H+ + HO- BOH + H+
• If both ions of the salt result from a weak acid, respectively base, then the
following reaction will take place with the water ions:
A- + B+ + H+ + HO- HA + BOH
• The reaction between the ions of a salt and the water ions is named
hydrolysis.
• Hydrolysis is a reversible reaction with the equilibrium more or less
displaced to the right, function of the dissociation grade, the solubility or
the volatility of the resulted compounds.
• Any time there is a difference between the dissociation grade of the acid or
the base that can result from the hydrolysis reaction, a variation of the
hydrogen or hydroxyl ion will take place, respectively a variation of pH.
Buffer solutions
• A buffer is a solution containing a mixture of a weak acid (HA) and its
conjugate base (A-) that is capable of resisting substantial changes in pH
upon the addition of small amounts of acidic or basic substances.
• Addition of an acid to a buffer leads to a conversion of some of the A- to the
HA form: -
A + H+ AH

-
• Addition of a base leads to a conversion A- of
of some + the
H HA
O to the A- form:
AH + HO 2

• As a result, addition of either acid or base leads to a change in the A- / HA


ratio. In the Henderson - Hasselbalch equation, which applies to buffer
systems, the ratio A- / HA appears as a logarithmic function. Hence,
[
changes in the A- / HA ratio lead to only minor
working range of the buffer.pH = pK + log
A− ] changes in pH within the
[ HA]
• A buffer’s working range is determined by the pK value of the
system.
• Specifically, it falls within +1
1 pH unit from the pK value.
value Beyond
that range, both of the buffer forms are not enough to allow the
buffer to function effectively when either acid or base is added.
• Buffer capacity depends on the volume of the buffer and on the
concentrations of the two buffer components. Buffer capacity is
usually defined as the number of equivalents of either H+ or OH-
that is required to change the pH of a given volume of buffer with
1 pH unit. That is:

Buffer capacity = dn / dpH

• where dn
n = equivalents of hydrogen or hydroxide ions added
• dpH
pH = change in pH produced by the addition of dn equivalents of
hydrogen or hydroxide ions
Selection of biochemical buffers
• Ideally, all the biochemical investigation must be done in aqueous buffer
solutions.. The natural medium of biomolecules and cellular organelles is under
a strict pH control.
• After the extraction of these components from cells, they must be maintained
in a medium with controlled pH, with the value in the interval 6 – 8. It is also
known the fact that many enzymatic processes consumes or product hydrogen
ions, the intervention of a buffering system being necessary to maintain the
pH constant.
• Only occasionally there are needed buffering systems with other pHs.
• The buffers use for biological determinations must fulfill a series of properties:
• pK between 6 and 8
• High solubility in water, but limited solubility in organic solvents
• To have a minim contribution to the number of ions in the medium
• No passing through biological membranes or the effect to be minim
• Minim salt effect
• no interaction with metallic ions of biological importance or to form well defined
complexes.
• Minim absorbency in VIS and UV
• Chemical stability
• Easy accessibility in pure forms.
Compound Abbreviation MW pK1 pK2 pK3 pK4

N-(2-acetamido)-2-
ACES 182.2 6.90 - - -
aminoethansulfonic acid
N-(2-acetamido)-2-iminodiacetic
ADA 212.2 6.60 - - -
acid
Acetic acid 60.1 4.76 - - -
Arginine Arg 174.2 2.17 9.04 12.48 -
Barbituric Acid 128.1 3.79 - - -
N,N-bis(2-hydroxyethyl)-2-
BES 213.1 7.15 - - -
aminoethansulfonic acid
N,N-bis(2-hydroxyethyl)glycine BICINE 163.2 8.35 - - -
Boric acid 61.8 9.23 12.74 13.80 -
Citric acid 210.1 3.10 4.75 6.40 -
Ethylendiaminotetracetic acid EDTA 292.3 2.00 2.67 6.24 10.88
Formic acid 46.03 3.75 - - -
Fumaric acid 116.1 3.02 4.39 - -
Glycine Gly 75.1 2.45 9.60 - -
Glycylglycine 132.1 3.15 8.13 - -
N-2-hydroxyethylpiperazine-N’-2-
HEPES 238.3 7.15 - - -
ethansulfonic acid
N-2-hydroxyethylpiperasine-N’-3-
HEPPS 252.3 8.00 - - -
propansulfonic acid
Hystidine His 209.7 1.82 6.00 9.17 -

Imidasol 68.1 6.95 - - -


2-(N-morfolino)- ethansulfonic acid MES 195.0 6.15 - - -

3-(N-morfolino)- propansulfonic
MOPS 209.3 7.20 - - -
acid
Phosphoric acidc 98.0 2.12 7.21 12.32 -
Succinic acid 118.1 4.18 5.60 - -
3-tris(hydroxymethyl)-
TAPS 243.2 8.40 - - -
aminopropansulfonic acid
N-tris(hydroxymethyil)methyl-2-
aminoethansulfonic acid TES 229.2 7.50 - - -

N-Tris(hydroxymethyl)
Tricine 179.0 8.15 - - -
methylglycine
Tris(hydroxymethyl)amino-methan Tris 121.1 8.30 - - -
Preparation of buffer solutions
• A buffer may be prepared in two ways:
• Known amounts of the A- and HA forms may be mixed and diluted to
volume.
• To a known amount of the HA form (A- form) a known amount of base
(acid) may be added and the mixture diluted to volume.
• Note that the molarity of a buffer always refers to the total concentration
of the buffer species.
• Thus, a 0.5M H2PO4- / HPO4-2 buffer is one in which the sum of the
concentrations of H2PO4- and HPO4-2 is 0.5 moles per liter.

pH = pK + log
[ A ] −

[ HA]
• pKa = 4.76 for acetic acid
• pH homeostasis in human organisms maintains:
pH = 7.4 ± 0.05
• Modifications of the acidic – basic balance
⇒ acidity if pH < 7.35
⇒ basicity if pH > 7.45
• The buffer system CO2 / HCO3- has a very important role in pH maintaining.
• Part of CO2 is dissolved in blood and reacts with water:
CO2 + H2O ⇔ H2CO3

• Carbonic acid is unstable and dissociates:


H2CO3 ⇔ H+ + HCO3- so CO2 + H2O ⇔ H+ + HCO3-

• pKa = 6.1 ⇒ 7.4 = 6.1 + log[HCO3-] / [CO2] ⇒ 1.3 = log[HCO3-] / [CO2]

• ⇒ 20 = [HCO3-] / [CO2]
• ⇒ [HCO3-] = 24 mM and [CO2] = 1.2 mM (pCO2 = 40 mmHg)
• [CO2] ↑ or [HCO3-] ↓ ⇒ acidosis
• [CO2] ↓ or [HCO3-] ↑ ⇒ alkalosis

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