Equilibrio Químico

Equilibrium is a state in which no changes are

observed over time.

Chemical Equilibrium: occurs when

 The speeds of the direct and inverse reactions are equalized
 Reagent and product concentrations remain constant

Physical Equilibrium
Equilibrium is a dynamic process
H2O (l) H2O (g)

Chemical quilibrium
N2O4 (g) 2NO2 (g)
 N2O4 (g) 2NO2 (g)

equilibrium
equilibrium
equilibrium

Start with NO2 Start with N2O4 Start with NO2 & N2O4
 Mass Action Law
In 1863 Guldberg & Waage they derived a constant of equilibrium by defining
equilibrium as the condition in which the speed of reactions forward and in reverse is
equal. And it is proportional to the "active masses"
aA + bB cC + dD
[C]c[D]d
K=
[A]a[B]b K = Equilibrium Constant
Mass Action Law: For a reversible reaction in
in equilibrium and at a constant temperature, a relationship
Determined concentrations of reagents and products
has a constant value k
Information offered by k
K >> 1 Scroll right Promote products
K << 1 Scroll Left It favors reactants
 Types of equilibriums
Equilibrium Reaction Equilibrium Constant
Acid-base dissociation HA + H2O H3O + A- Ka Acid Dissociation constant
Solubility MA M+n A-n Kps Solubility product
Complex Formation M+n + aLb- MLa (n- Kf Formation constant
ab)+

Oxidation/ eduction reaction Ared + Box Aox + Bred Keq Reaction equilibrium
constant
Phase distribution (cast) AH2O Aorgánico KD Distribution /
distribution coefficient
 Homogeneous equilibrium applies to reactions in which all reactive
species are in the same phase.

dinitrogen tetroxide N2O4 (g) 2NO2 (g) Nitrogen dioxide

or nitrogen tetraxide
[NO2]2 PNO
2
Kc = Kp =
2
[N2O4] PN O
2 4
[ A ] = Molar Concentration of A

In many cases PV = nRT

P = (n/V) RT
Kc  Kp
aA (g) + bB (g) cC (g) + dD (g)
n = number moles
Kp = kc(RT) Dn
R = ideal Gas cons

Dn = moles de productos (g) – moles de reactivos (g)

Dn = (c + d) – (a + b)
 Equilibrio Homogéneo
CH3COOH (ac) + H2O (l) CH3COO- (ac) + H3O+ (ac)

[CH3COO-][H3O+]
K‘c = [H2O] = constante
[CH3COOH][H2O]

[CH3COO-][H3O+]
Kc = = K‘´c [H2O]
[CH3COOH]
 Ejemplo
2NO(g)+ O2(g)  2NO2(g) HF(ac) + H2O(l)  H3O+ + F -1

kc 
 NO2 
2

kc
'  H O  F 
3
 1

 NO.  2  O2   HF   H 2O

kp 
2
PNO 2
kc 
 H O  F 
3
 1

2
PNO PO2  HF 
Example:
Carbonyl Chloride (COCl2), also called phosgene (used in the First World War
as a poisonous gas) for the reaction of obtaining phosgene reached
equilibrium when the concentration of: [CO] = 1.2 x 10-2 M [Cl2] = 0.054 M
and [COCl2] = 0.14 M. Calculate the equilibrium constant.

CO(g) + Cl2 (g) COCl2 (g)

Kc 
 COCl2 
Kc 
 0.14
 CO.   Cl2  1.2 x102.   0.054

Kc  216.05
EJERCICIO
The equilibrium constant Kp obtained for the decomposition of phosphorus
pentachloride is 1.05 at 250 ° C.
PCl5 (g)  PCl3 (g) + Cl2 (g)
If in the equilibrium the partial pressures of in the equilibrium for PCl5 and
PCl3 are 0.875 atm and 0.463 atm respectively. What is the partial pressure in
equilibrium for Cl2 at that temperature?

P P 1.05 
(0.463)( P )
Kp 
Cl 2
PCl 3 Cl 2

(0.875)
P PCl 5

(1.05)(0.875)
P   1.98atm
(0.463)
Cl 2
 Example

For the reaction: N2 (g) + 3H2 (g)  2NH3 (g)

Kp is 4.3 x 10-4 at 375 ºC . Calculate Kc
Dn
Kp  Kc ( RT )
Dn = (c + d) – (a + b) Kp
Kc  Dn
Dn = (2) – (1 + 3) ( RT )
4
4.3x10
Kc  ( 24)
(0.0821 (273  375)
Equilibrio Heterogéneo
It occurs in reactions in which reagents and products are in
different phases.

CaCO3 (s) CaO (s) + CO2 (g)

[CaO][CO2] [CaCO3] = constante

K‘c = [CaO] = constante
[CaCO3]
[CaCO3]
Kc = [CO2] = K‘c x Kp = PCO2
[CaO]

The concentration of a solid and a pure liquid is not

included in the expression of the equilibrium constant (its
value in 1)
For the following Equilibrium at 295 K:
NH4HS (s) NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265 atm.
Calculate Kp and Kc for the reaction
[ NH 3 ][ H 2 S ]
Kc 
[ NH 4 HS ]

Kp = PNH PH S =( 0.265atm) (0.265atm) = 0.0702 atm

3 2

Kp = Kc(RT)Dn

Kc = Kp(RT)-Dn
Dn = 2 – 0 = 2 T = 295 K

Kc = 0.0702 x (0.0821 x 295)-2 = 1.20 x 10-4

Equilibrium Multiple
 Equilibrium constants for species that dissociate or combine

(weak and precipitated electrolytes)

 Applies to reactions in which products are reactive in a

subsequent reaction.
[C][D] [E][F]
A+ B C+D K´c K‘c = K‘‘c =
[A][B] [C][D]
C+D E + F K‘c‘
A+ B E+F Kc [E][F]
Kc =
[A][B]
Kc = Kc´Kc´´
If a reaction can be expressed as the sum of two or more
reactions, the equilibrium constant for the overall reaction
will be given by the product of the individual equilibrium
constants.
N2O4 (g) 2NO2 (g) 2NO2 (g) N2O4 (g)

[NO2]2 [N2O4] 1
Kc= = 4.63 x 10 -3
Kc -1
= = = 216
[N2O4] [NO2] 2 k

When an equation is written in the opposite direction,

the equilibrium constant is the reciprocal of the original
constant.
 What information is obtained from
the equilibrium constant?
• Inform where the balance shifts
• Predict the direction in which a reaction will proceed.
• It allows to calculate the concentration of reagents and
products once equilibrium is reached.
The reaction quotient (Qc) measures the relative amounts of products and reactants present
during a reaction at a particular point in time. The reaction quotient aids in figuring out which
direction a reaction is likely to proceed, given either the pressures or the concentrations of the
reactants and the products. The Qc value can be compared to the Equilibrium Constant, (K), to
determine the direction of the reaction that is taking place.
 Prediction of the direction of the reaction.
The Reaction Quotient (Qc) is calculated, substituting the
initial concentration of the reagents and products in the
expression of the equilibrium constant (Kc).
 Qc> kc the system proceeds from right to left to reach equilibrium.
 Qc = kc the system is in balance
 Qc < kc the system proceeds from left to right to reach equilibrium.
The Reaction Quotient (Qc) is calculated, substituting the
initial concentration of the reagents and products in the
expression of the equilibrium constant (kc).
aA + bB  cC + dD

[C ] [ D]
C d

Qc  0 0

[ A] [ B]
a

0
b

[A]0 = Concentración inicial

Liquid and Aqueous

• To calculate Qc:

• Write the expression for the reaction quotient.

• Find the molar concentrations or partial pressures of each species involved.
• Substitute values into the expression and solve.
 The equilibrium constant is Kc = 6.5 x 10-4 at 35 ° C for the formation of
nitrosyl chloride, a yellow-orange compound from nitric oxide and molecular
chlorine
2NO(g) + Cl2 (g)  2NOCl(g)
In one experiment, 0.02 moles of NO, 0.0083 moles of Cl2 and 6.8 moles of
NOCl are mixed in a 2.0 L flask.

0.02 mol NO [ NOCl ]02

[ NO]   0.01M
2L Qc 
[ NO]02 [Cl 2]10
0.0083 mol Cl2
[Cl2 ]   0.00415M
2L
(3.4) 2
6.8 mol NOCl Qc  2
 27.8 x10 6
[ NOCl ] 
2L
 3.4M (0.01) (0.00415)
27.8 x 10 6  6.5 x 10 4 Reaction moves
towards to
Qc  kc Reagents
 Factors that alter the chemical equilibrium
In 1884 the French chemist Henry-Louis
Le Châtelier
Principio de Le Châtelier
If an external force is applied to a system in
equilibrium, the system will adjust to regain
equilibrium.

 Changes in Concentration

N2 (g) + 3H2 (g) 2NH3 (g)

The balance
shifts to the left Añade
to restore NH3
balance
 Decrease
Increase Concentration
Concentration of A
of A

pressure
According to Le Châtelier, if the pressure is increased, the position of equilibrium will move so
that the pressure is reduced again. Pressure is caused by gas molecules hitting the sides of
their container. The more molecules in the container, the higher the pressure will be. The
system can reduce the pressure by reacting in such a way as to produce fewer molecules.
Increase
Pressure

Example 1: Haber Process

N2 (g) + 3H2 (g) 2NH3 (g)

If this mixture is transferred from a 1.5 L flask to a 5 L flask, in which direction does
a net change occur to return to equilibrium?
SOLUTION
Because the volume is increased (and therefore the pressure reduced), the shift
occurs in the direction that produces more moles of gas. To restore equilibrium
the shift needs to occur to the left, in the direction of the reverse reaction.

N2 (g) + 3H2 (g) 2NH3 (g)

Decreasing the pressure
The equilibrium will move in such a way that the pressure increases again. It can do
that by producing more gaseous molecules. In this case, the position of equilibrium
will move towards the left-hand side of the reaction.

Summary of Pressure Effects

Three ways to change the pressure of an equilibrium mixture are:
1. Add or remove a gaseous reactant or product,
2. Add an inert gas to the constant-volume reaction mixture,
3. Change the volume of the system.
 Increasing the temperature
If the temperature is increased, then the position of equilibrium will move so that the
temperature is reduced again. Suppose the system is in equilibrium at 300°C, and the
temperature is increased 500°C. To cool down, it needs to absorb the extra heat
added. In the case, the back reaction is that in which heat is absorbed. The position of
equilibrium therefore moves to the left. The new equilibrium mixture contains more A
and B, and less C and D.

If the goal is to maximize the amounts of C and D formed, increasing the temperature
on a reversible reaction in which the forward reaction is exothermic is a poor
approach.
Decreasing the temperature?
The equilibrium will move in such a way that the temperature increases again. Suppose the system is in
equilibrium at 500°C and the temperature is reduced to 400°C. The reaction will tend to heat itself up again to
return to the original temperature by favoring the exothermic reaction. The position of equilibrium will move to
the right with more A and B converted into C and D at the lower temperature:
Catalysts
Adding a catalyst makes absolutely no difference to the position of equilibrium,
and Le Châtelier's principle does not apply. This is because a catalyst speeds up the
forward and back reaction to the same extent and adding a catalyst does not affect
the relative rates of the two reactions, it cannot affect the position of equilibrium.
Silver(I) diammine cation
 Principio de Le Châtelier
 Change in concentration
addition Agrego
Elimination
Elimino
aA + bB cC + dD

Change Equilibrium shifts

Left (reagents)
Increase in the concentration of product (s)
Decrease in the concentration of product (s) Right (products)
Increase in reagent concentration (s)
Decrease in reagent concentration (s) Right (products)
Left (reagents)
 Principio de Le Châtelier

Change in Volume and Pressure

A (g) + B (g) C (g)

Change Equilibrium shifts

Increase pressure Side of lower # moles of gas
Decrease the pressure Side of highest # moles of gas
Increase volume Side of highest # moles of gas
Decrease volume Side of lower # moles of gas
 Principio de Le Châtelier

Change in Temp

Change Rxn. Exothermic Rxn. Endothermic

Temperature rise Disadvantages Favors
Temperature decreases Favors Disadvantages

Add a Catalyst
 does not change K
 equilibrium is reached more quickly
 Procedure to obtain the equilibrium constant
The experimental data:
Are they values in equilibrium?
No
Yes
moles Concentration of at least one
M  member in equilibrium and
L initial concentration
Calculate the Molar
concentration or Partial
Relate initial concentrations to
Pressure of each compound
equilibrium

Replace in the expression of

equilibrium constants [C]c[D]d PCc PDd
kC= kp=
aA + bB  cC + dD [A] [B]
a b
PAa PBb
 2 NOCl(g) 2 NO(g) + Cl2(g)
2.00 moles of NOCl are added in a 1.00 L flask. In equilibrium the [NO] is 0.66 mol / L.
Calculate K.

Build a concentration table

[NOCl] [NO] [Cl2]

Initial 2.00 0 0
Equilibrium Change
0.66
2 NOCl(g) 2 NO(g) + Cl2(g)
2.00 moles of NOCl are placed in a 1.00 L flask. In equilibrium the
[NO] is 0.66 mol / L. Calculate K.

Build a concentration table

[NOCl] [NO] [Cl2]

Inicio 2.00 0 0
Cambio -0.66 +0.66 +0.33
Equilibrio 1.34 0.66 0.33
2 NOCl(g) 2 NO(g) + Cl2(g)
[NOCl] [NO] [Cl2]
Inicio 2.00 0 0
Cambio -0.66 +0.66 +0.33
Equilibrio 1.34 0.66 0.33

[NO]2[Cl2]
K
[NOCl]2
2 NOCl(g) 2 NO(g) +
Cl2(g)
[NOCl] [NO] [Cl2]
Inicio 2.00 0 0
Cambio -0.66 +0.66 +0.33
2
Equilibrio 1.34 [NO] [Cl2]0.33
0.66
K
[NOCl]2

[NO]2[Cl2] (0.66)2(0.33)
K = = 0.080
[NOCl]2 (1.34)2
Ejemplo:
A mixture of 3.9 moles of NO and 0.88 moles of CO2 was
reacted in a one liter (1L) flask at a certain temperature
according to the reaction:
NO(g) + CO2 (g)  NO2 (g) + CO(g)

It was found that 0.11 moles of CO2 were present in the

equilibrium. Calculate the equilibrium constant Kc of the
reaction:
Cálculos para obtener la Constante de equilibrio
Por estequiometría

NO(g) + CO2(g)  NO2(g) + CO(g)

Inicio 3.9 0.88
moles
Cambio
moles
Equilibrio 0.11
moles
Conc. M
V=1L
Calculations to obtain the equilibrium constant
By stoichiometry

NO(g) + CO2(g)  NO2(g) + CO(g)

Inicio 3.9 0.88
moles
Change - 0.77
moles
Equilibrium 0.11
moles
Conc. M
V=1L
Cálculos para obtener la Constante de equilibrio
Por estequiometría

NO(g) + CO2(g)  NO2(g) + CO(g)

Inicio 3.9 0.88
moles
Cambio - 0.77 - 0.77 + 0.77 + 0.77
moles
Equilibrio 0.11
moles
Conc. M
V=1L
Cálculos para obtener la Constante de equilibrio
Por estequiometría
NO(g) + CO2(g)  NO2(g) + CO(g)
Inicio 3.9 0.88
moles
Cambio - 0.77 - 0.77 + 0.77 + 0.77
moles
Equilibrio 3.13 0.11 0.77 0.77
moles
Conc. M
V=1L
Cálculos para obtener la Constante de equilibrio
De acuerdo a la estequiometría

NO(g) + CO2(g)  NO2(g) + CO(g)

Inicio 3.9 0.88
moles
Cambio - 0.77 - 0.77 + 0.77 + 0.77
moles
Equilibrio 3.13 0.11 0.77 0.77
moles
Conc. M 3.13 mol 0.11 mol 0.77 mol 0.77 mol
1L 1L 1L 1L
V=1L 3.13 M 0.11 M 0.77 M 0.77 M
 NO(g) + CO2 (g)  NO2 (g) + CO(g)

kc 
 NO2   CO.  Se sustituyen los valores

 NO.   CO2  calculados

Kc 
 0.77  0.77
 1.722
 3.13  0.11
 Substances A and B react as follows to produce C and D:

The equilibrium constant K has a value of 0.30. Assume that 0.20 mol of A and
0.50 mol of B is dissolved in 1.00 L, and the reaction is carried out. Calculate
concentrations of reagents and products in equilibrium.

Sol: The initial concentration of A is 0.20 M, and that of B is 0.50 M, while those of C and D
they are initially 0 M. When the reaction has reached equilibrium, the concentrations
of A and B will have decreased and those of C and D will have increased. Let x be the
concentration of equilibrium of C or the moles / liter of A and B that react. How a mole of D is
obtained With each mole of C, the concentration of D will also be x. Concentration can be
represented initial of A and B as the analytical concentrations, CA and CB. Concentrations
of equilibrium are [A] and [B]. The concentrations of A and B will decrease each
at x, that is [A] = CA-x and [B] = CB-x. So that equilibrium concentrations they will be:
This is a quadratic equation and can be solved algebraically by the formula quadratic given
in Appendix B:

0.0121/0.0351 = 0.345
Instead of using the quadratic equation, the approximation method can be used
successive In this procedure initially x is neglected compared to the initial
concentrations to simplify the calculations, and an initial value of x is calculated.
Then you can use this first estimate of x to subtract it from CA and CB and thus give
an estimate Initial equilibrium concentration of A and B, and calculate a new x. The
process Repeat until x is essentially constant.

First calculation

Calculations converge faster if an additional digit is retained throughout the

process.
Cálculo de concentraciones en el
equilibrio

• Tenemos la Constante de
equilibrio de la reacción
• Tenemos las concentraciones
iniciales
• Utiliza la variable “x” para
representar los cambios de
concentración
• Despeje para obtener el
valor de “x”
• Calcule las concentraciones
de todas las especies
 H2(g) + I2(g) 2 HI(g), Kc = 55.3
paso 1. defina las concentraciones en el
EQUILIBRIO
[H2] [I2] [HI]
Inicio 1.00 1.00 0
Cambio
Equilib
 Calculation of equilibrium concentrations
A mixture of 0.500 moles of H2 and 0.500 moles of I2 is placed in a
stainless steel vessel of 1.00 L at 430 ° C. The equilibrium constant
kc for the reaction is 54.3 at this temperature. Calculate the
concentrations of H2, I2 and HI in the equilibrium.
H2 (g) + I2 (g)  2 HI(g)

H2 I2

Cantidad inicial 0.500 0.500

moles
M = moles/V (L) 0.500 mol/ 1 L 0.500 mol/ 1 L

Con. M 0.500 0.500

Cálculo de concentraciones en el equilibrio
H2 (g) + I2 (g)  2HI(g)
Inicio 0.500 0.500 0.000
M
Cambio
M
Equilibrio
M
Procedure for calculating concentrations in
equilibrium
H2 (g) + I2 (g)  2HI(g)
Inicio 0.500 0.500 0.000
M
Cambio -x -x + 2x
M
Equilibrio (0.500-x) (0.500-x) 2x
M
 Procedimiento para el Cálculo de
concentraciones en el equilibrio
H2 (g) + I2 (g)  2HI(g)
Inicio 0.500 0.500 0.000
M
Cambio -x -x + 2x
M
Equilibrio (0.500-x) (0.500-x) 2x
M

 HI 
2
54.3 
 2x
2

kc 
 H2   I2   0.500  x   0.500  x 
 Procedimiento para calcular las
concentraciones en el equilibrio

54.3 
 2x
2

 0.500  x   0.500  x  0.617796/0

54.3 
 2x 2

54.3 
 2x  7.37
 0.500  x  2
 0.500  x 
x  0.393M

[H2] = (0.500-0.393) M = 0.107 M

[I2] = (0.500-0.393) M = 0.107 M
[HI] = 2 x 0.393 M = 0.786 M
 A 12800C la constante de equilibrio (Kc) para la reacción:
Br2 (g) 2Br (g)

Es 1.1 x 10-3. Si las concentraciones iniciales son [Br2] =

0.063 M y [Br-] = 0.012 M, calcule la concentración de las
especies en el equilibrio.

Br2 (g) 2Br- (g)

Inicial (M) 0.063 0.012
ICE Cambio (M) -x +2x
Equilibrio (M) 0.063 - x 0.012 + 2x

[Br]2 (0.012 + 2x)2

kc = kc = = 1.1 x 10-3 Solve for x
[Br2] 0.063 - x
 (0.012 + 2x)2
kc = = 1.1 x 10-3
0.063 - x
4x2 + 0.048x + 0.000144 = 0.0000693 – 0.0011x
4x2 + 0.0491x + 0.0000747 = 0
x =
-b ±  b 2
– 4ac
ax + bx + c =0
2
2a
x = -0.0105 x = -0.00178
Br2 (g) 2Br (g)
Initial (M) 0.063 0.012
Change (M) -x +2x
Equilibrium (M) 0.063 - x 0.012 + 2x

At equilibrium, [Br] = 0.012 + 2x = -0.009 M or 0.00844 M

At equilibrium, [Br2] = 0.062 – x = 0.0648 M
Equilibrio Ácido-
Base
Importance :

 The acidity or basicity of a solution is an

important factor in chemical reactions.
 In the use of buffers of a given pH to maintain
the pH of the solution at a desired level.
 To understand acid-base titrations.
 The effects of acids on species and reactions,
for example, the effects of complexation or
precipitation
 Physiological buffers
Definiciones :
Arrhenius theory (1894)

ACID:
Any substance that produces protons in aqueous solution.

HA + H2O H3O+ + A-

BASE: HCl + H2O H+ + Cl-

Any substance that produces hydroxide ions in aqueous

solution.
B + H2O BH+ + OH-

M(OH)n → Mn+ + nOH-

NaOH + H2O Na+ + OH-

J. Am. Chem. Soc., 36 (1912) 353

 Teoría de Bronsted-Lowry (1923)

Arrhenius theory (1894)

This theory mentions that an acid is any substance that a
proton can donate, and a base is any substance that a proton
can accept.
And you can write a "half reaction“
ácido = H +
+ base Pares conjugados

 Acido Donador de protones

 añade H+ al disolvente

 Base Aceptor de protones

 elimina H+ del disolvente
 Teoría de Lewis (1923)

Lewis introdujo la teoría electrónica de los ácidos y las bases.

Acido : sustancia que puede aceptar un par de electrones

Base sustancia que puede donar un par de electrones

(generalmente contiene un oxígeno o un nitrógeno como
donador de electrones)
Ácidos y bases comunes

Acidos Fórmula Molarity

 Nítrico HNO3 16
 Clorhídrico HCl 12
 Sulfúrico H2SO4 18
 Acético CH3COOH 18
Bases
 Hidróxido de amonio NH4OH 15
 Hidróxido de sodio NaOH sólido
 Hidróxido de potasio KOH sólido
 Acidos Bases

 Frutas cítricas Jabón

 Aspirina Detergentes
 Coca Cola Limpiadores amoniacales
 Vinagre Fármacos estomacales
 Vitamina C
Acid Characteristics
One of the characteristic properties of ACIDS is their ability
to react with metals and produce hydrogen

Zn + 2 HCl ZnCl2 + H2
Some metals react with acids better than others.

Iron Zinc Magnesium

 Reactivity
potassium
potassium They react violently with cold water
sodium
sodium
Calcium
Calcium React slowly with cold water
Incremento de reactividad

magnesium
magnesium
aluminum They react very slowly with water
aluminum
zinc enough acid reagents
zinc
chromium
chromium
iron
iron
nickel
nickel They react moderately with high levels
tin
tin of acids
lead
lead
copper
copper
silver
silver They are not reactive in acids
platinum
platinum
gold
gold
 Características de las Bases
Una de las propiedades características de las BASES es que
reaccionan con los ácidos para producir una sal.
Es lo que se conoce como reacción de neutralización.

NaOH + HCl NaCl + H2O

La neutralización de las ácidos grasos en la piel produce jabón ,
y por eso las bases son resbaladizas al tacto.

Cuando un ácido reacciona con una base forma sal más agua

KOH + HNO3 KNO3 + H2O

 Equilibrios ACIDO-BASE acuosos

Cuando un ácido o una base se disuelve en

agua se disocia, o ioniza, y el grado de
ionización depende de la fuerza del ácido.

 Un electrólito “fuerte” se disocia por completo

 Un electrolito “débil” se disocia de manera
parcial.
 Electrólitos
Aqueous solutions of certain compounds
conduct electricity because they have
positive and negative ions

Aqueous solution

si Conduct no
electricity

Electrolyte No electrolyte
 Strong electrolytes
Strong acids are strong electrolytes, they dissociate completely

HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)

H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)

 Electrolitos fuertes
Strong Bases are strong electrolytes, they dissociate completely

LiOH, RbOH, CsOH, Ca(OH)2, Sr(OH)2

H 2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)

H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
 Weak electrolytes

Weak electrolytes - do not dissociate completely

CH3COOH CH3COO- (aq) + H+ (aq)

 Weak acids are weak electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)
H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)
H2CO3, H2S

Weak bases are weak electrolytes

NH3 (aq) + H2O(l)  NH4+ (aq) + OH- (aq)

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)
CH3NH2, C6H5NH2, C5H5N
Ácidos fuertes y débiles
 Electrólitos débiles

En los electrólitos débiles, a la constante de

equilibrio se le llama:
Constante de disociación

2H2O  H3O+ + OH-

Kw = [H3O+ ][OH-]
Tipos de electrólitos
Fuertes Débiles
HCl HC2H3O2 (ácido acético)
HClO4 NH3
aH2SO4 C6H5OH (fenol)
HNO3 HCHO2 (ácido fórmico)
NaOH C6H5NH2 (anilina)
NaC2H3O2

a El primer protón se ioniza por completo en solución diluida, pero el

segundo protón se ioniza parcialmente (Ki 10-2).
 Producto iónico del agua Kw
El agua es una sustancia anfótera que puede actuar como un
ácido o como una base.

HC2H3O2(aq) + H2O(l) H3O+ + C2H3O2-(aq)

ácido base ácido base

H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)

ácido base ácido base
 Autoionización del agua
El agua pura se ioniza ligeramente, o sufre autoprotólisis:

Las moléculas de agua reaccionan entre ellas para formar iones.

H2O(l) + H2O(l) H3O+(aq) + OH-(aq)

(10-7M) (10-7M)

Kw = [ H3O+ ] [ OH- ] = 1.0 x 10-14 @ 25oC

 Escala de pH
In 1909 Soren-Sorgensen, proposed a method to express
the acidity of a solution.
He defined the term called pH (power of the hydrogen ion)

Kw = [ H3O+ ] [ OH- ] = 1.0 x 10-14 @ 25oC

pKW = pH + pOH = 14

pH = -log[H+] [H+]= [H3O+]

pOH = -log[OH-] [OH]= [OH-]

Escala de pH y pOH

pH  7 la disolución es BASICA

pH = 7 la disolución es NEUTRA

pH  7 la disolución es ACIDA
Escala de
pH
Acid ionization percentage
(degree of dissociation)

HA + H2O  H3O+ + A-

[H3O+] desde HA
Grado de ionización =
[HA] inicial

[H3O+] desde HA
% de ionización = x 100
[HA] inicial
 Relación de las constantes

KW  K a K b

KW
Ka 
Kb

KW
Kb 
Ka

Apéndice 3 del Libro “Fundamentos de Química analítica”. ´Capitulo No. 9

 Cálculo de pH
Ácidos Fuertes

HCl(aq) + H2O(l) H3O+ (aq) + Cl-(aq)

disolución 0.1 M [H3O+]= 0.1 M

pH = -log [H3O+]

pH = -log [0.1]

pH = 1
Calcular el pH de una solución 2 x 10-3 M HNO3

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)

HNO3 es un ácido Fuerte – 100% disociado.

[H+] = 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.70

pH = 2.7
 Cálculo de pH
Bases fuertes

NaOH(ac) + H2O(l) Na+(ac) + OH-(ac)

Solución 0.1 M NaOH [OH-] = 0.1 M

pOH = -log [OH-] pOH = -log [0.1]

pOH = 1

pH + pOH = 14
pH = 14 - pOH = 14-1

pH = 13
Calcular el pH de una solución 1.8 x 10-2 M Ba(OH)2

Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)

Ba(OH)2 es una base fuerte – 100% disociado.

[OH-] =0.018 M x 2 = =.036M

pOH = -log [0.036]

pH = 14.00 – pOH = 14.00 -1.44 = 12.56

pH = 12.56
Cual es la concentración de iones OH- en una solución de
HCl cuya concentración de iones de hidrógeno es 1.3 M?

Kw = [H+][OH-] = 1.0 x 10-14

[H+] = 1.3 M

Kw 1 x 10 -14
[OH-] = = = 7.7 x 10 -15
M
[H ]
+
1.3

[OH-] = 7.7 x 10 -15 M

El pH de una muestra de lluvia ácida en cierta región del
norte de México en un día particular fue de 4.82. Cuál es
la concentración de iones H+ de la lluvia ácida?
pH = -log [H+]

[H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M

La concentración de iones OH- de una muestra de sangre

es muy baja y es de 2.5 x 10-7 M. Cuál es el pH de la
sangre?
pH + pOH = 14.00
pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60

pH = 14.00 – pOH = 14.00 – 6.60 = 7.40

pH = 7.40
Strong Acid Weak Acid
 Ley de Acción de
Masas

Para una reacción general

aA(ac) + bB(ac)  cC(ac) + dD(ac)

La constante de equilibrio es:

[C ]c [ D] d
K
[ A] a [ B ]b
[ ] Concentraciones molares en el equilibrio
Constante de ionización de un ácido débil

base ácido
Ácido base conjugada conjugado
CH3COOH + H2O  CH3COO- + H3O+

[CH3COO-][H3O+]
Kc =
[CH3COOH][H2O]

[CH3COO-][H3O+]
Ka= Kc = = 1.8x10-5
[CH3COOH]
Cálculos de pH para Ácidos Débiles
CH3COOH + H2O CH3COO- + H3O+

Solución 0.1 M
[CH3COO-][H3O+]
K a= = 1.8x10-5
[CH3COOH]
Como: [CH3CO2-] = [H3O+]
[H3O+]2
ka=
[CH3COOH]
despejando
:
 [ H 3O  ]  K a [CH 3COOH ]
[ H 3O ]  K a [ Ácido]

[ H 3 O  ]  1.8 x10 5  [0.1] [H3O+] = 0.00134

pH = -log [H3O+] pH = -log [0.00134] pH = 2.87

 [CH3COO- ][H3O+]
Ka =
[CH3COOH] –[H3O+]

Si Ka es menor o igual a 10-4

Tenemos : [CH3CO2H] >>> [H3O+]

[CH3COO- ][H3O+]
ka=
[CH3COOH]

10-8< Ka < 10-4

Cuál es el pH de una solución de HF 0.5 M @ 250C?
-
[H +
][F ]
HF (aq) -
H (aq) + F (aq)
+ Ka = = 7.1 x 10-4
[HF]
HF (aq) H+ (aq) + F- (aq)
Inicial (M) 0.50 0.00 0.00
Cambio (M) -x +x +x
Equilibrio (M) 0.50 - x x x
x2
ka = = 7.1 x 10-4 ka << 1 0.50 – x  0.50
0.50 - x
x2
ka  = 7.1 x 10-4 x2 = 3.55 x 10-4 x = 0.019 M
0.50
[H+] = [F-] = 0.019 M pH = -log [H+] = 1.72
[HF] = 0.50 – x = 0.48 M
 Constante de ionización de una base
acido base
base acido conjugado conjugada
NH3 + H2O NH4+ + OH-

[NH4+][OH-]
Kc =
[NH3][H2O]

[NH4+][OH-]
Kb = = 1.8x10-5
[NH3]
Valores de Ka y Kb para ácidos y bases débiles:
- Son siempre valores menor que 1
- Un ácido con una mayor Ka es más fuerte que otro cuya K a sea menor.
- Una base con una mayor Kb es más fuerte que otra cuya Kb sea menor.
 Cálculos de pH Bases Débiles
NH3 + H2O NH4+ + OH-

[NH4+][OH-] = 1.8x10-5
Kb =
[NH3]
[OH  ]  K b [ Base]
Como: [NH4+] = [OH-]
despejando
[OH-]2
Kb =
: [OH  ]  K b [ NH 3 ]
[NH3]

[OH  ]  1.8 x10 5  [0.1]

[OH  ]  0.00134

pOH = -log [OH-] pOH = -log [0.00134] pOH = 2.87

pH = 14 - pOH = 14-2.87 pH = 11.13

 Cálculos de pH
Tipo de sustancia

Ácido Base

Fuerte Débil Fuerte Débil

pH = -log [H3O ]
+ pOH = -log [OH-]

pH = 14 - pOH

[ H 3O  ]  K a  [ HA] [OH  ]  K b  [ Base]

 Ácidos Dipróticos y
Polipróticos
 Muchos ácidos y bases son polifuncionales, tienen más
de un protón o un ion hidróxido ionizable.
 Estas sustancias se ionizan por etapas, y para cada uno
de ellos se escribe una constante de equilibrio
Ácidos
dipróticos H2CO3
H2CO3 ↔ H+ + HCO31-
HCO31- ↔ H+ + CO32-

[H+]Total = [H+]1 + [H+]2

K a1 
 HCO   H 
1
3

K a2 
 CO   H 
2
3


 H 2 CO3   HCO 
1
3

Ka1 = 4.7 x 10-7 K a2= 4.4 x 10-11

 Ácidos dipróticos
Ejemplo: Calcular el pH de una solución de H2CO3 0.1 M
H2CO3 ↔ H+ + HCO31- Ka1 = 4.7 x 10-7 De
tablas
HCO31- ↔ H+ + CO32- Ka2
[H+]Total = [H+]1 + [H+]2 = 4.4 x 10-11
Considerando

K a1 
 HCO   H 
1
3
 [H+] = [HCO31-]

 H 2 CO3  [H2CO3] = 0.1 - [H+]

Como Ka1 muy pequeña

H 

1  K a1  H 2 CO3   4. 7 x10 7
  0. 1  2.145 x10 4

pH = 3.668
 Ejemplo: Calcular el pH de una solución de H2CO3 0.1 M

H2CO3 ↔ H+ + HCO31- Ka1 = 4.7 x 10-7

HCO31- ↔ H+ + CO32- Ka2
[H+]Total = [H+]1 + [H+]2 = 4.4 x 10-11
 CO   H 
[H+] = [CO32-]
2 
[HCO31-] = 2.144 x 10-4 - [H+]
K a2  3

 HCO  1
3
Como Ka2 muuuy pequeña

H 

2  
 K a 2 HCO31  4.4 x10 11   2.145 x10  4   9.714 x10 8

[H+]Tot = [H+]1 + [H+]2 = 2.144 x 10-4 + 9.714 x 10-8 = 2.1449 x 10-4

pH = 3.668
Ácido sulfúrico: Un ácido diprótico.

H2SO4 + H2O H3O+ + HSO4- Ka1 = muy grande

HSO4- + H2O H3O+ + SO42- Ka2 = 1.96

 Ácidos polipróticos
Conclusiones:
Considerando: Ka1 >>> Ka2>>>>>Ka3

Tenemos: [H+]1 >>> [H+]2

Por lo tanto: [H+]Total = [H+]1

El pH solo depende de la primera disociación.

Los valores de Ka de las diferentes etapas de los ácidos
polipróticos se hacen progresivamente más pequeños porque la
carga negativa va incrementándose y hace más difícil la
disociación del siguiente protón
 Ácidos polipróticos
Ácido fosfórico: Un ácido triprótico.

H3PO4 + H2O H3O+ + H2PO4- Ka1 = 1.1x10-2

H2PO4- + H2O H3O+ + HPO42- Ka2 = 7.5 x10-8

HPO42- + H2O H3O+ + PO43- Ka3 = 4.8x10-13

La ionización total [H+]t es la suma de estos pasos individuales,

y la constante de ionización total es el producto de las
constantes individuales de ionización

Ka = Ka1Ka2Ka3 = 4.0 x 10-22

pKa = 1.96, 7.12 y 12.32