Professional Documents
Culture Documents
Chemical Kinetics Water Water Chemical Kinetics Water Water
Chemical Kinetics Water Water Chemical Kinetics Water Water
Chemical Kinetics Water Water Chemical Kinetics Water Water
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:
CH3CH2OH → CH =CH + H O
Al2O3
2 2 2
→
Cu
→
CH3CH2OH CH3CH=O + H2
• 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
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
-
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
• 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
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
HPO4 + H+
2
H2PO4
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 ] +
+
Ka K a2
[H ] = − + + Kac
2 4
-
• Addition of a base leads to a conversion A- of
of some + the
H HA
O to the A- form:
AH + HO 2
• 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 -
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
• ⇒ 20 = [HCO3-] / [CO2]
• ⇒ [HCO3-] = 24 mM and [CO2] = 1.2 mM (pCO2 = 40 mmHg)
• [CO2] ↑ or [HCO3-] ↓ ⇒ acidosis
• [CO2] ↓ or [HCO3-] ↑ ⇒ alkalosis