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Dynamic equilibrium

 The equilibrium in general may be physically or


chemically.
Physical equilibrium
Vaporization and Condensation
Experiment: If water in a closed vessel is heated we notice that two opposite processes
happen, vaporization and condensation:
1. On starting heat the vaporization process occurs, so vapour pressure increases.
* Water vapour pressure:
Is the pressure due to water vapour in air at a certain temperature.
2. Then vaporization process continues until vapour pressure equals saturated water
vapour pressure.
*Saturated water vapour pressure:
Is the maximum water vapour pressure in air at a certain temperature.
- At equilibrium: the rate of vaporization equals the rate of condensation:
Vaporization
Water (liquid)
Condensation water (vapour)

- The type of equilibrium in the previous experiment is known as “Equilibrium system”


 Equilibrium system: it is apparently a stationery system but in reality dynamic.

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.)

(b) Incomplete (Reversible) chemical reaction:


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It is the reaction that occurs in both forward and backward. i.e. in the two
directions.
*Give reason for:
Incomplete (reversible) chemical reaction occurs in two directions.
Because both of the reactants and the products are found in the medium of the reaction,
so the products combine with each other to reform the reactants.
Example:
CH3COOH(aq)+ C2H5OH(aq) CH3COOC2H5(aq) + H2O(l)
Acetic acid ethyl alcohol ethyl acetate ester
*Chemical equilibrium:
"It is a dynamic system takes place when the rate of forward reaction equals the
rate of backward reaction".
* During chemical equilibrium:
1- The equilibrium state is a stationary system apparently, but a dynamic system in reality.
2- All reactants and products are still found in the medium of reaction.
3- The concentration of the reactants and the products are not changed.
4- The conditions of the reaction (such as temperature and pressure) are not changed.
5- State of equilibrium may be reached slowly or rapidly.
Complete (irreversible) reaction Incomplete (reversible) reaction
* It occurs in one direction only. * It occurs in forward and backward directions
* Some of products escape from medium *Both reactants and products are still found in
of reaction (gas evolves or precipitate). the medium of reaction.
* The products cannot combine with each *The products can combine with each other to
other to reform the reactants. reform the reactants.
* such as: NaCl(aq) + AgNO3(aq) *Such as: CH3COOH + C2H5OH
NaNO3(aq) + AgCl(s) CH3COOC2H5 + H2O
 Rate of chemical reaction:
It is the rate of change in concentration of reactants or products per unit time.
-The concentration unit: mole / liter or M and the time unit: minute or second.
 During the complete (irreversible) chemical reaction: Concentration
*Concentration of reactants decreases to minimum value. Products
*Concentration of products increases to maximum value.

Reactants
Time
 During the incomplete (reversible) chemical reaction before equilibrium:
*Concentration of reactants decreases. Concentration

*Concentration of products increases. Reactants

Products

Time

 During reversible chemical reaction at equilibrium: Concentration


*Concentration of reactants decreases till reach constant
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value at the state of equilibrium.
Reactants
*Concentration of products increases till reach constant
Products
value at the state of equilibrium.

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

*Concentration of products decreases.

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

R2 = K2 [C]c [D]d where K2 is the rate constant.


At equilibrium state;
The rate of forward reaction (R1) equals the rate of backward reaction (R2).
R1 = R 2 at equilibrium state.
K1 [A]a [B]b = K2 [C]c [D]d
K1 = [C]c [D]d
K2 [A]a [B]b
Ratio K1 / K2 is a constant value called equilibrium constant (Kc) for the reaction.

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).

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*The concentration of water or pure solid substances is not written (G.R).
Because its values are constant and fixed at any concentration.
Example (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.

FeCl3 (aq) + 3NH4SCN(aq) Fe(SCN)3(aq) + 3NH4Cl (aq)


Yellowish colourless blood red

KC [Fe (SCN)3] [NH4Cl]3


=
[FeCl3] [NH4SCN]3

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.

BiCl3(aq) + H2O(l) BiOCl(aq) + 2HCl(aq)


Colourless colourless white colour colourless

[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.

CO(g) + H2O(l) CO2(g) + H2(g)


2NO(g) + O2 2NO2(g)
4NH3(g) + 3O2(g) 2N2(g) + 6H2O(l)
`
Solution:-
c = [CO2] [H2]
KC =
[CO]
c = [NO2]2
KC =
[NO]2 [O2]
= [N2]2
KC =
[NH3]4 [O2]3

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Gas – phase Equilibria

* 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.

aA(g) + bB(g) cC(g) + dD(g)

PcC PdD
Kp =
PaA PbB
Example:-
Preparation ammonia gas in industry from its elements:-

High pressure, cooling


N2(g) + 3H2(g) 2NH3(g) H= -92KJ

*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

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Reaction equilibria that involve different physical states of matter are known as
"Heterogeneous Equilibria".

aA(s) + bB(g) cC(s) + dD(g)


We expect:

[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

"Change in any of the condition of a chemical reaction at equilibrium state


[such as concentration, temperature or pressure], the reaction will be shifted
in the opposite direction of this change".
 Factors affecting a chemical reaction already in a state of equilibrium:
1) Concentration. 2) Temperature. 3) Pressure.
(1) Effect of concentration:
a) Increasing concentration of reactants or decreasing concentration of products:
The reaction shifts to direction of formation of products (forwards).
b) Decreasing concentration of reactants or increasing concentration of
products:
The reaction shifts to direction of formation of reactants (backwards).

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.

FeCl3 (aq) + 3NH4SCN(aq) Fe(SCN)3(aq) + 3NH4Cl (aq)


Yellowish colourless blood red

*When adding an excess amount of iron III chloride to the solution, the
intensity of red colour increases (G.R).

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Due to the formation of excess amount of iron III thiocyanate as the reaction moves
in the forward direction.
*When adding an excess amount of ammonium chloride, the intensity of the
blood red colour decreases (G.R).
Due to decomposition of iron III thiocyanate as the reaction moves to backward
direction.
Experiment (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.
BiCl3 + H2O BiOCl + 2HCl
Colourless colourless white colour colourless
*When adding an excess amount of water to the solution, the intensity of white
colour increases (G.R).
Due to the formation of excess amount of bismuth oxychloride as the reaction moves
in the forward direction.
*When adding an excess amount of hydrochloric acid, the intensity of the
white colour decreases (G.R).
Due to the decomposition of bismuth oxychloride as the reaction moves to backward
direction.
(2) Effect of temperature:
a) If the reaction is exothermic : R P + Heat or R P, H = -ve
*The increase in temperature shifts the reaction in the backwards direction.
*The decrease in temperature shifts the reaction in the forward direction.

b) If the reaction is endothermic : R+ Heat P or R P, H = +ve


*The increase in temperature shifts the reaction in the forward direction.
*The decrease in temperature shifts the reaction in the backwards direction.

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Experiment;

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.

2- Flask becomes colourless when it is cooled (G.R).


Because the decrease in temperature shifts the reaction in the forward direction
forming colourless N2O4.
3- Flask becomes reddish brown colour when it is in hot water (G.R).
Because the increase in temperature shifts the reaction in the backwards direction
forming reddish brown NO2.
(3)Effect of pressure :
*If volumes (no of molecules) of the reactants = volumes (no of molecules) of the
products; No effect of pressure on the equilibrium.
* When the volumes of reactants > the volumes of products:-
a) Increasing the pressure: The reaction shifts to direction of products (forwards).
b) Decreasing the pressure: The reaction shifts to direction of reactants
(backward).
*When the volumes of products > the volumes of reactants:
a) Increasing the pressure: The reaction shifts to direction of reactants (backward).
b) Decreasing the pressure: The reaction shifts to direction of products (forwards).
Decr. pressure
Incr.2NO
pressure
2 2NO + O2
2 moles 3 moles
N.B:
Heating cylinders of butagas from out side is very dangerous (G.R).
Because heating process converts the butagas from the liquefied state to the
gaseous state so, the volume of the gas increases and causes high pressure on the
cylinder walls leading to its explosion.

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 arises only in weak electrolytes (G.R).


Because the solutions of weak electrolytes contain free ions and non ionized molecules.
AB A+ + B-
Weak

 Ionic equilibrium not arises in strong electrolytes (G.R).


Because their solutions are completely ionized, so contain free (+ve) & (-ve) ions only.
AB A+ + B-
Strong

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-

*There are no positive hydrogen ions or protons in solution of acids (G.R).


Because when the acid is ionized in water, the positive proton is linked with molecule
of water with coordinate bond to form hydroxonium ion (H3O)+ ;
H+ + H2O H3O+

The Solubility Product Constant


An ionic solid introduced into a polar solvent dissociates into its component ions:

AmBn(s) mAn+(aq) + nBm -(aq)


* By applying the law of mass action for a dissolution process at equilibrium:

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

Questions on chapter ten

I. Write the scientific expression of each of the following:


1- A system stationary static apparently and in reality is dynamic.
2- A substance increases the rate of a chemical reaction without a change in its
chemical composition.
3- Reaction proceed in one direction yielding products do not react to give again the
initial reactants.
4- If an equilibrium system is upset by a change in one of the factors influences it
such as concentration, pressure and temperature, the system activates in the
direction in which this change is minimized.
5- Changes in concentration of reactants in unit of time.
6- The rate of the chemical reaction is directly proportional to the active masses of
the reacting substances (giving) that temperature remains constant.
7- The minimum amount of energy that must be gained by a molecule to react at
collision.
II. Give reasons:-
1- Sodium chloride solution is a strong electrolyte, while acetic acid solution is a
weak electrolyte.
2- The catalyst does not effect on equilibrium reaction.
3- The reaction between silver nitrate and sodium chloride is a complete one.
4- The reaction of ethanol and acetic acid is a reversible one.
5- Low of mass action can be applied on the weak electrolytes.
5- In summer food goes rotten quickly if we left in the air.
6- Food is cooked quickly in pressure cookers.
7- Catalysts have an economical importance.
8- The butagas cylinder should not be heated to obtain the gas rapidly.
9- Common salt solution in water passes electricity while sugar solution does not.

III. Define the following:

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1- Law of mass action. 2- Activation energy.
3– The ionic product of water. 4- Catalyst.
5–Rate of chemical reaction. 6- Le chatelier's principle.
IV. Compare between complete ionization and weak ionization.
V. What are the factors which effect on the equilibrium chemical reaction.
VI. Complete:
1- At constant temperature, the rate of chemical reaction is ………..proportional to
the active mass of the reacting substance.
2- In the following equilibrium reaction;
3H2 (g) + N2 (g) NH3
Concentration of ammonia is increased when the amount of hydrogen or nitrogen
………………………..

VII.In the reversible reaction at equilibrium state:-


3H2 + N2 2NH3 + Energy
(A) Give reasons:-
1-The crease in the rate of forward reaction by increase in pressure.
2-The reaction goes in the backward reaction by increase in temperature.
(B) What is the effect of each of the following on the amount of ammonia products:
1- Increase in the temp. 2-Adding of more nitrogen.
3- Removal of ammonia from the system. 4-Increase in pressure.

VIII.In the following equilibrium chemical reaction:


FeCl3 + 3NH4SCN Fe (SCN)3 + 3NH4Cl
Red blood colour
What happens to the concentration of Fe (SCN)3 when we add…………
a) An Excess amount of ammonium thiocyanate.
b) An Excess amount of ammonium chloride.

IX. In the following equilibrium chemical reaction.


BiCl3 + H2O BiOCl + 2HCl
What happens to the white colour of BiOCl , when
a) We add excess water to the reaction medium.
b) Remove an amount of H2O from the reaction medium.

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