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Chemical equilibrium
Types of chemical reactions;
(a) Complete (Irreversible) chemical reaction:
It is reaction that occurs in one direction only. I.e. (direction of formation of
products).
*Give reason for:
Complete (Irreversible) chemical reaction occurs in the direction of formation of
products only.
Because one of the products escapes from the medium of the reaction in from of gas or
precipitate, so the products cannot recombine with each other to form reactants.
Examples:
1- Fe(s) + 2HCl(aq) dil. FeCl2(aq) + H2(g)
2- NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl(s) (white ppt.)
Reactants
Time
During the incomplete (reversible) chemical reaction before equilibrium:
*Concentration of reactants decreases. Concentration
Products
Time
Time
During the incomplete (reversible) chemical reaction on shifting forward:
Concentration
*Concentration of reactants decreases.
Products
*Concentration of products increases.
Reactants
Time
During the incomplete (reversible) chemical reaction on shifting backward:
Concentration
*Concentration of reactants increases. Reactants
Products
Time
During the incomplete (reversible) chemical reaction on adding catalyst:
Forward reaction
The catalyst does not affect on the position of equilibrium
as it increases the rate of both the backward and forward
reactions by the same proportion, so it decreases only the
time needed to reach the equilibrium state
Reversible reaction
Law of mass action
*The Norwegian scientists Waage and Guldberg discovered the law of mass action
which controls the relation between velocity of the chemical reaction and
concentration of the reactants.
Law of mass action: -
“At constant temperature, the rate of chemical reaction is directly proportional
to the product of multiplication of the reactant concentration; each is raised to
the power of the number of molecules or ions in the balanced chemical
equation”.
* To understand the law of mass action we must study the following reaction:-
aA + bB cC + dD
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Where;
* A , B , C and D are different substances presents in the reaction.
*a , b , c and d are any whole number for the molecules of the substance in a
balanced chemical equation.
Forward reaction: R1 α [A]a [B]b
R1 = K1 [A]a [B]b where K1 is the rate constant.
Backward reaction: R2 α [C]c [D]d
Kc
Kc= [C]c [D]d
[A]a [B]b
*The equilibrium can be reached from the backward direction:
cC + dD aA + bB
K' = 1 ÷ Kc
c
[C]c [D]d = [A]a [B]b
K' 1 ÷ =
c
[A]a [B]b [C]c [D]d
N.B:-
* The concentration of products or reactants is in moles / liter and designated by
their formulas in square brackets [ ].
* If the value of equilibrium constant is less than one (very small value); this indicates
that the equilibrium is shifted to the backward direction. (Concentration of products is
less than the concentration of reactants).
* If the value of equilibrium constant is very large, this indicates that the equilibrium is
shifted to the forward reaction will go to near completion. (Concentration of products
is more than the concentration of reactants, so most of reactants changed into
products).
Example (2);
On adding water to bismuth III chloride “colourless”; the solution becomes the
colour of the solution changes to white colour (G.R).
Due to the formation of bismuth oxychloride which has white colour.
[BiOCl] [HCl]2
KC =
[BiCl3]
Example (1);
Calculate the equilibrium constant of the following reaction:
H2 + I2 2HI
Given that at equilibrium, the concentration of iodine, hydrogen and hydrogen iodide
are 0.221, 0.221 and 1.563 mole / liter.
Solution:-
c = [HI]2 (1.563)2
KC = = = 50
[H2] [I2] 0.221 X 0.221
Example (2):-
Examine the equilibrium constant given for the following reaction, which goes forward
completion. Explain your reason.
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s) Kc = 2 X 1015
Solution:-
*Since the equilibrium constant is the result of dividing the concentration of the
products by the concentration of the reactants.
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*The value of equilibrium constant is large (more than one) this means that the
reaction proceeds in the forward direction as the concentration of the products is
very large than concentration of reactants, so, the reaction proceed in the forward
direction.
Example (3):-
Examine the equilibrium constants given for the following reaction, which goes
backward explain your reason.
AgCl(s) Ag+(aq) + Cl-(aq) ,Kc = 1.7 X 10-10
Solution:-
*Since the equilibrium constant is the result of dividing the concentration of the
products by the concentration of the reactants; Kc = [Ag+] [Cl-]= 1.7 X 10-10
*The value of equilibrium constant is a small value (less than one), this means that
the concentration of products is less than the concentration of the reactants so, the
reaction proceed in the backward direction.
Example (4):-
Calculate the equilibrium constant of the following reaction:-
N2O4 (g) 2NO2 (g)
Given that at equilibrium, the concentration of N2O4 = 0.213, NO2 = 0.0032 mole/liter.
Solution:-
c = [NO2]2 [0.0032 ]2
KC = = = 4.81 X 10-5
[N2O4] 0.213
Example (5):-
Write the equilibrium constant Kc for each of following reactions.
* If the substance which enter the reaction or resulted from the reaction found in
gaseous state, we express about them by using their partial pressures.
PcC PdD
Kp =
PaA PbB
Example:-
Preparation ammonia gas in industry from its elements:-
*Four molecules from the reactants (1molecule of nitrogen and three molecules of
hydrogen) react to from two molecules from ammonia gas.
* The formation of ammonia gas is accompanied by decrease in the number of
molecules and so decrease in their volume and pressure.
*From the previous example we observe that if the equilibrium state reached and
pressure is then increased, the reaction is shifted in the direction of decreasing
pressure in which volume is less (according to le chatelier‘s principle).
= P2NH3
Kp =
PN2 P3H2
Kp is used to express the equilibrium constant in the gaseous reaction and also, can
be expressed by the concentration molarity.
Example :
Calculate the equilibrium constant (KP) of the following reaction;
N2(g) + 2O2(g) 2NO2(g)
Given that the pressures are 2 atmospheric air, 1 atmospheric air and 0.2
atmospheric air for the substance NO2, O2 and N2 respectively.
Solution:-
P2NO2 22
Kp = = = 20
PN2 P O22
0.2 X (1)2
Heterogeneous Equilibria
[C]c [D]d
Kc =
[A]a [B]b
But the molarity of solid compound like A (also pure liquids) is just its density
divided by its molar mass which is a constant that is characteristic of A. Thus the
numerical value of [A] and [C] is subsumed into the equilibrium constant:
[D]d
K'c =
[B]b
Le chatelier's principle
Experiment (1);
On adding solution of iron III chloride "yellowish" to ammonium thiocyanate
solution “colourless”; the solution becomes blood red colour (G.R).
Due to the formation of iron III thiocyanate which has blood red colour.
*When adding an excess amount of iron III chloride to the solution, the
intensity of red colour increases (G.R).
Coolimg
2NO2 N2O4 + Heat
Heating
Reddish brown Colourles
1- Get a flask containing nitrogen dioxide (NO2) gas which has a reddish brown
colour at room temperature.
Ionic equilibrium
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*Types of solution according to their conductivity;
(1) Non – electrolytic solution:
Non – electrolytic Solutions don't conduct electricity (G.R).
Because they are free from ions (non ionized). e.g; Oils, Kerosene and sugar solution.
(2) Electrolytic solutions:
Electrolytic solutions conduct electricity (G.R).
Because their solutions contain free (+ve) and (-ve) ions.
Types of Electrolytic solutions;
Strong electrolytes Weak electrolytes
Completely ionized in their solution e.g; Partially ionized in their solutions e.g ;
*Strong acids; (HCl, H2SO4, HNO3) *weak acids ;( CH3COOH, H2CO3, ..)
*Strong alkalis; (NaOH-KOH-Ca(OH)2). *weak alkalis ;( NH4OH Al(OH)3,.,)
Ionic equilibrium:
It is the equilibrium arises in weak electrolytes between non-ionized molecules
and their ions.
Experiment:-
1- When the electric current passes through a pure acetic acid dissolved in benzene
or hydrogen chloride gas dissolved in benzene;
We notice that, the lamp in both cases will not light (G.R).
Because they are not ionized so neither of the two liquids contain ions thus do not
conduct the electric current.
2-When the electric current passes through equal concentration of acid solution of
0.1 mole of hydrogen chloride gas dissolved in one liter of water (hydrochloric acid)
and 0.1 mole of pure acetic dissolved in one liter of water.
We notice that;
*In the case of hydrochloric acid the lamp gives a strong illumination (G.R).
Because it contains a large number of ions, So good conductor to electricity.
*In the case of acetic acid, the lamp gives a faint (weak) illumination (G.R).
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Because it contains a small number of ions. So it is a bad conductor to electricity.
3- On dilution of both pervious solutions becoming 0.01 mole then 0.001 mole and
test for effect on the conductivity of electric current.
We notice that;
*Illumination of the lamp is not affected by dilution of hydrochloric acid (G.R).
Because it is completely ionized in its aqueous solution.
* Illumination of the lamp increases by the dilution of acetic acid (G.R).
Because the ionization of acetic acid increases by increasing of dilution as its
unionized molecules are ionized gradually.
The ionization of these two acids can be written as:-
HCl + H2O H3O+ + Cl-
CH3COOH H3O+ + CH3COO-
K sp = [An+]m [Bm-]n
(The concentration of solid AmBn(s) approximately still constant.)
The solubility product of any partially soluble ionic compounds:
“Is the multiplication of the concentration of its ions which are found in
equilibrium state with its saturated solution”.
N.B:
For a saturated solution:
K sp = [An+]m [Bm-]n
For a unsaturated solution:
K sp < [An+]m [Bm-]n
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For a super saturated solution:
K sp > [An+]m [Bm-]n
Example:
If degree of solubility of AgCl is 10-5 mole/liter. Calculate the solubility product of AgCl.
Solution:
AgCl Ag+ + Cl-
Ksp = [Ag+] [ Cl-]
Ksp = 10-5 X 10-5 = 10-10 mol/L