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Chemical Equilibrium (CURRENT) - CN
Chemical Equilibrium (CURRENT) - CN
Chemical Equilibrium (CURRENT) - CN
Chemical Equilibrium
CHAPTER 9:
CHEMICAL EQUILIBRIUM (REVERSIBLE REACTIONS)
9.1 Introduction
Some reactions can occur from either direction. This means that products can either be
converted to reactants or reactants converted products. Such reactions are called reversible.
Definition: A reversible reaction is a reaction in which the products of the reaction can react
or decompose to form the initial reactants under suitable conditions.
When reversible reactions occur in a closed system, they gradually attain a state of dynamic
equilibrium with time. A reversible reaction is not necessary a reaction in dynamic equilibrium
unless it takes place in a closed system with both the forward and backward reactions occur at
the same rate. Dynamic means continues to occur without stopping. Equilibrium in this context
means the concentrations or partial pressures of reactants and products remain constant with
time due to forward and backward reaction occurring at the same rate. The sign “⇌” in a
chemical reaction indicates that the reaction is reversible or in equilibrium. Chemical reactions
such as W + X ⇌ Y + Z, with the sign “⇌” between the reactants and the products are called
reversible reactions or equilibrium reactions.
Definition: A dynamic chemical equilibrium is a state in a reversible reaction in a closed
system where the concentrations of the reactants and the products are constant as a result of
equal rate of forward and the reverse reactions.
Thus characteristics of dynamic equilibrium are:
- Both the reactants and the products are present in the system at any given moment
- The equilibrium can be attained beginning with only products or reactants in a closed
system at a given condition.
- At equilibrium, all measurable or observable properties of the system such as
concentrations, partial pressures, colour intensity, temperature etc remain constant.
- The rate of forward reaction is equal to the rate of the reverse reaction.
- If the forward reaction is exothermic, then the backward reaction will be endothermic
and vice versa.
- At equilibrium, concentration or partial pressures of reactants and products remain
constant but not necessary the same under a given condition like temperature, catalyst.
- Catalyst has no effect on equilibrium position.
- Equilibrium is indefinite unless an external factor disturbs it.
The following conditions are necessary for a system to attain chemical equilibrium:
- The system must be closed
- The chemical reaction must be reversible.
Examples of reversible reactions that attain equilibrium in a closed system
CaCO3(s) ⇌ CaO(s) + CO2(g), 2SO2(g) + O2(g) ⇌ 2SO3(g), N2(g) + 3H2(g) ⇌ 2NH3(g).
Definition: An equilibrium mixture is the mixture of constant amounts of reactants and
products in a system which is in a state of dynamic equilibrium.
The concentrations or partial pressures of reactants and products remain constant at
equilibrium because the rate of the forward reaction is equal to the rate of the backward
reaction. For a chemical reaction such as R(g) ⇌ P(g) or R(aq) ⇌ P(aq), at equilibrium, the
amounts of reactant (R) and product (P) may be the same as illustrated in Fig 9.1a or
different as illustrated in Fig 9.1b and Fig 9.1c below.
concentration
concentration
concentration
P P R
R R P
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Chemical Equilibrium
In each of the graphs above, equilibrium is attained at time “t”. When → is used between
reactants and products, it implies that the reverse reaction is not possible or rarely achieved
e.g. H+(aq) + OH– (aq) → H2O(l).
Equilibrium mixture is also called equilibrium composition.
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Chemical Equilibrium
Kc for the forward reaction H2(g) + I2(g) ⇌ 2HI(g) is and for the
and respectively.
Where [Y]eq is the concentration of product ‘Y’ at equilibrium, (PY)eq is the partial pressure
of product ‘Y’ at equilibrium, ‘a’, ‘b’, ‘c’ and ‘d’ are the number of moles of ‘W’, ‘H’, ‘Y’
and ‘Z’ respectively in the stoichiometric balance equation. For the Kc expression, ‘W’, ‘H’,
‘Y’ and ‘Z’ are either all gases or all in their aqueous forms. For the Kp expression, ‘W’,
‘H’, ‘Y’ and ‘Z’ can only be all gaseous since Kp only applies to a species in the gaseous
state.
Law: The equilibrium law states that for a reversible reaction at equilibrium, the product
of the molar concentrations of the products raised to their stoichiometric coefficients
divided by the product of molar concentrations of the reactants raised to their
stoichiometric coefficients in a balanced equation is a constant at constant temperature.
, units of Kc = = (moldm-3)c + d - a - b.
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Chemical Equilibrium
atmospheres (atms).
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Chemical Equilibrium
1. (a) 1 mole of HI(g) is allowed to dissociate in a 1dm3 vessel at 440°C. Only 0.78 mol of
HI(g) were left at equilibrium. What is the equilibrium constant of this reaction at 440°C?
(b) if 2 mol of H2(g) and 1 mol of I2(g) are mixed together in a 1dm3 vessel at 440°C,
how may moles of HI(g), H2(g) and I2(g) will be present at equilibrium at 440°C?
(c) 1.2mol of I2(g) and 1.5mol of H2(g) are mixed in a 1dm3 closed system. After some time, the
equilibrium amount of HI(g) is found to be 1.6mol. Calculate Kc and state with an
explanation whether the equilibrium reaction was actually attained at 440°C or not.
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Chemical Equilibrium
Solution:
(a)
2HI(g) ⇌ H2(g) + I2(g)
I 1 0 0
C – 0.22 +0.11 +0.11
E 0.78 +0.11 +0.11
= 0.02.
= 50. =>
4x2 = 50(2 - 3x + x2) => 4x2 = 100 - 150x + 50x2 => 46x2 - 150x + 100 = 0.
It should be recalled that x cannot be 2.33 because equilibrium concentrations calculated using
2.33 will be negative values which are physically meaningless. So x can only be 0.93.
Thus moles of each species at equilibrium is given by:
H2(g) = 2 – 0.93 = 1.07mol, I2(g) = 1 – 0.93 = 0.07mol, H2(g) = 2(0.93) = 1.86mol.
(c) 2x = 1.6, so x = 0.8, (1.5-x) = 0.7 and (1.2-x) = 0.4
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Chemical Equilibrium
. => = Kc(RT)-2.
Exercises on Kp:
1. At equilibrium, the reaction: 2XY(g) ⇌ X2(g) + Y2(g) has a total pressure ‘PT’ at 50°C. Show that the
equilibrium constant (Kp) for the reaction at 50°C is 1/81 if degree of dissociation is 4/11.
2. At equilibrium, the reaction: 2XY(g) ⇌ X2(g) + Y2(g) has a total pressure ‘PT’ at 50°C.
Show that for the degree of dissociation ‘δ’, the equilibrium constant (Kp) for the equilibrium
reaction is independent of the total pressure (PT).
3. 1.0 mole of PCl5 vapour was heated to 500K in a sealed vessel. The equilibrium mixture, at a
pressure of 6.2 atm, contained 0.6 moles of chlorine. Calculate the value of K p and give the units
for Kp. The equation for the reaction: PCl5(g) ⇌ PCl3(g) + Cl2(g). Ans; Kp = 3.5atm.
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Chemical Equilibrium
4. At a certain temperature, and a total pressure of 0.95 atm, bromine vapour contains 45% by
volume of bromine atoms at equilibrium. The equilibrium equation is Br 2(g) ⇌ 2Br(g).
(a) Calculate Kp for the equilibrium
(b) At what total pressure (without temperature change) would the percentage (%) by volume of
bromine atoms be reduced to 30%?
(a) Since % by volume gives mole fraction, => PBr(g) = 0.45(0.95) = 0.43atm, PBr2(g) = 0.55(0.95)
= 0.52atm. => Kp = (0.43atm)2/0.52atm = 0.36 atm. Ans; (a) Kp = 0.36 atm.
(b) Let the total pressure = PT. Thus pBr(g) = 0.3(PT) = 0. 3PT, PBr2(g) = 0.7(PT) = 0.7 PT. => Kp =
(0.3 PT)2/0.7 PT = 0.36 atm. => 0.13 PT = 0.36atm, => PT = 0.36/0.13 = 2.77 atm. (b) PT = 2.77
atm
Exercises on Kp and Kc:
1. Some equilibrium reactions (Eqm I, Eqm II and Eqm III) with their respective equilibrium
constants at a given temperature (T°C) are given below.
Eqm reaction I: N2(g) + O2(g) ⇌ 2NO(g), KcI = 5.0 x 10-31.
Eqm reaction II: 2NOCl(g) ⇌ 2NO(g) + Cl2(g), KcII = 4.7 x 10-4 moldm-3.
Eqm reaction III: N2(g) + 3H2(g) ⇌ 2NH3(g), KcIII = 9.1 x 105mol-2dm6.
(a) Calculate the equilibrium constant (Kc) at the at the same temperature (T°C) for the
reaction: 2NH3(g) + O2(g) + Cl2(g) ⇌ 2NOCl(g) + 3H2(g).
(b) Why are the units of equilibrium constant not given for the equilibrium reaction I?
(c) Suggest the Kp value for the equilibrium reaction I if temperature of the system is
maintained at (T°C). State a reason for the value of Kp suggested.
2.
Answers:
1. (a) Ans, Kc = 1.2 x 10-33moldm-3.
(b) Number of moles of gaseous products equal to number of moles of gaseous reactants.
(c) Kp = 5.0 x 10-31 since number of moles of gaseous products equal to number of moles of
gaseous reactants.
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Chemical Equilibrium
This is a type of equilibrium in which all the species in the equilibrium reaction are not in the
same phase e.g. 3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g).
9.5 Le Chatelier’s Principle and Factors Affecting Equilibrium
A stress or constrain (concentration, pressure and temperature) on a reaction at equilibrium causes a
change on the equilibrium position but not on the equilibrium constant. Temperature is the only
stress or constrain that affects both the equilibrium position and the equilibrium constant.
The effect of each stress can be explained using Le Chatelier’s principle.
Principle: Le Chatelier’s principle states that when a system at equilibrium is subjected to a
constrain, the system responds in a way that counteracts or opposes the constraint.
∆Ea
is because a catalyst increases the rates of the forward and
EaR backward reactions equally. The activation energies of both
catalysed the forward and backward reactions are reduced by the same
path magnitude in the presence of a catalyst. A catalyst can only
reduce the time taken for a reaction to reach equilibrium but
Reaction path has no effect on a reaction already at equilibrium.
EaF = activation energy for forward reaction, EaR = activation energy for backward (reverse)
reaction, ∆Ea = Change (decrease) in activation energy in the presence of a catalyst.
Act03:
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Chemical Equilibrium
(a) The equation for the industrial manufacture of ammonia (Haber process) is given below.
N2(g) + 3H2(g) ⇌ 2NH3(g); ΔH = -92 kJmol-1.
What will be the effect on the position of equilibrium and yield of ammonia if the following changes
are applied to the system? Explain.
(i) Temperature of the system is increased. The equilibrium position will shift to the left
(endothermic direction) to remove heat added since the forward reaction is exothermic. In this
case, yield of ammonia reduced.
(ii) The pressure of the system is decreased. The equilibrium position will shift to the left since the
total number of moles of gaseous reactants is more the total number of moles of gaseous
products. In this case, yield of ammonia reduced
(iii) Concentration of nitrogen gas is increased by pumping more nitrogen into the system. The
equilibrium position will shift to the right so as to consume the added amount of nitrogen for
equilibrium to be restored. In this case, yield of ammonia increased.
(iv) Concentration of ammonia gas is increased by pumping more ammonia into the system. The
equilibrium position will shift to the left so as to consume the added amount of ammonia for
equilibrium to be restored. In this case, yield of ammonia reduced.
(v) Concentration of hydrogen gas is decreased. The equilibrium position will shift to the left so as
to replace the amount of hydrogen removed for equilibrium to be restored. In this case, yield
of ammonia reduced.
(vi) Concentration of ammonia gas is decreased by liquefying the ammonia and tapping off from the
system. The equilibrium position will shift to the right so as to replace the amount of
ammonia removed for equilibrium to be restored. In this case, yield of ammonia increased.
(vii) Iron catalyst is added to the system. No effect on the equilibrium position since the catalyst
speeds up rate of forward and the reverse reaction equally.
(b) Suggest possible changes in the industry to improve on the yield of ammonia. Frequently remove
the ammonia formed, increase concentration of reactants, decrease temperature of the system.
(c) The equation for the equilibrium reaction between iodine vapour and hydrogen at 440ºC is given
below.
I2(g) + H2(g) ⇌ 2HI(g); ΔH = -10.4 kJmol-1.
What will be the effect on the position of equilibrium if:
(i) The pressure of the system is increased? No effect on the equilibrium position since the total
number of moles of gaseous products is equal to the total number of moles of gaseous
reactants.
(ii) The pressure of the system is increased? The equilibrium position will shift to the right
(exothermic direction) to replace the heat removed since the forward reaction is exothermic.
(d) The equation for the equilibrium reaction between iron and steam is given below.
3Fe(s) + 4H2O(g) ⇌ Fe3O4(s) + 4H2(g),
What will be the effect on the position of equilibrium if the pressure of the system is increased? No
effect on the equilibrium position since the total number of moles of gaseous products is equal to
the total number of moles of gaseous reactants.
The table below give examples of stress on an equilibrium position and equilibrium constant.
Effect on equilibrium
Change Type of change (stress) Effect on equilibrium position
constant
Add reactant or remove
Moves to right No effect
product
Concentration
Add product or remove
Moves to left No effect
reactant
Increase pressure or Moves towards side with fewer gas
No effect
Pressure decrease volume moles
(or volume) Decrease pressure or Moves towards side with more gas
No effect
increase volume moles
Moves in endothermic direction Increases (if H = +ve)
Increase temperature
(right if H = +ve, left if H = -ve) Decreases (if H = -ve)
Temperature
Moves in exothermic direction Decreases (if H = +ve)
Decrease temperature
(left if H = +ve, right if H = -ve) Increases (if H = -ve)
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Chemical Equilibrium
THE NEN SERIES A-Level chemistry notes 2023-2024 school year prepared by Nkemzi E.N