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(PHYCHEM) Module 2 - Chemical Equilibrium

The document discusses chemical equilibrium, including its characteristics, the law of mass action, and the equilibrium constant expressions. It explains the Haber-Bosch process as an example of a reversible reaction and outlines the impact of temperature and pressure on equilibrium in industrial processes. Additionally, it covers the Van't Hoff isotherm and provides examples for calculating equilibrium constants and predicting reaction directions.

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13 views34 pages

(PHYCHEM) Module 2 - Chemical Equilibrium

The document discusses chemical equilibrium, including its characteristics, the law of mass action, and the equilibrium constant expressions. It explains the Haber-Bosch process as an example of a reversible reaction and outlines the impact of temperature and pressure on equilibrium in industrial processes. Additionally, it covers the Van't Hoff isotherm and provides examples for calculating equilibrium constants and predicting reaction directions.

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ANALYTICAL CHEMISTRY:

CHEMICAL EQUILIBRIUM
P R E P A R E D B Y : E N G R . L . A . A G U S T I N
C H E D E P A R T M E N T

C S U - C O E A
CONTENT OUTLINE
• Review of Chemical Equilibrium
• Le Chatelier’s Principle in Industrial Processes
• Van’t Hoff Isotherm
• Temperature Dependence of Equilibrium Constant: Van’t Hoff Reaction Isochore
REVERSIBLE REACTION
→ a reaction which can go in the The Haber-Bosch Process
forward and backward direction
simultaneously Nitrogen and hydrogen gas react
with one another under high
pressure and temperature to form
A+B⇌C+D ammonia.

A + B → C + D (Forward Reaction)
C + D → A + B (Reverse Reaction)
CHEMICAL EQUILIBRIUM

- the dynamic state of a reversible


reaction when the two opposing
reactions occur
at the same rate
and the concentrations of
reactants and products do not
change with time.
CHARACTERISTICS OF CHEMICAL
EQUILIBRIUM
1. Constancy of concentrations: When chemical equilibrium is established, concentrations
of the various species in the reaction mixture (Equilibrium mixture) become constant
We write concentrations in equilibrium using brackets.

Example:

A gas mixture containing 1 g of Hydrogen (H 2) and 127g of


Iodine (I2) per liter has the equilibrium concentrations
[H2] = 0.5 and [I2] = 0.5

2. Equilibrium can be initiated from either side

3. Equilibrium can be attained in an open vessel


CHARACTERISTICS OF CHEMICAL
EQUILIBRIUM

4. A catalyst cannot change the equilibrium point (except


that it is achieved earlier): it enhances the rate of reaction
5. Value of Equilibrium constant does not depend upon the
initial concentration of reactants
6. At Equilibrium, ΔG = 0: The Gibbs free energy (G) is
minimum and any change taking place at equilibrium proceeds
withouht change in free energy.
LAW OF MASS ACTION
→“the rate of a chemical reaction is proportional to the active
masses of the reactants” *active mass – molar concentration (mols/L)
Consider the general reaction:
A+B⇌C+D
According to Law of Mass Action:
Rate of Forward reaction ∝ [A][B] = k1[A][B]
Rate of Reverse reaction ∝ [C][D] = k2 [C][D]
EQUILIBRIUM CONSTANT EXPRESSION FOR A
REACTION IN GENERAL TERMS

Consider the general reaction:


aA + bB ⇌ cC + dD
Where a, b, c and d are numerical quotient of the substance, A, B,
C, and D respectively.
k1 𝐶 𝑐 𝐷 𝑑
= 𝑎 𝑏
k2 𝐴 𝐵
At equilibrium, any specific temperature, k1/k2 is constant.
The equilibrium constant is For heterogenous equilibria,
therefore: (an equilibrium system in which
reactants and products exist in two or
𝑐 𝑑 more states of matter)
𝐶 𝐷
Kc = 𝑎 𝑏
𝐴 𝐵 The concentrations of pure solids and
liquids are not included in the
equilibrium constant expression.
in terms of partial pressures of gases,
→ This is because the concentrations
of pure solids or liquid is fixed and
(𝑃𝐶𝑐 )(𝑃𝐷
𝑑
)
Kp = cannot vary.
(𝑃𝐴𝑎 )(𝑃𝐵
𝑏)
EXAMPLE:
Write the equilibrium constant expression for the synthesis of
ammonia:

N2 (g) + 3H2 (g) ⇌ 2NH3 (g)

Try this:
N2O5 (g) ⇌ NO2(g) + O2 (g)
EXAMPLE:
RELATIONSHIP OF KC AND KP
Kp = Kc (RT) Δn
Where:
Δn = difference in the sums of the coefficient for the gaseous products and reactants
R = gas constant
Kp = Equilibrium gas constant in terms of pressure
Kc = Equilibrium gas constant in terms of concentration

*assuming all gases constituting the equilibrium mixture obey the ideal gas equation
EXAMPLE:
At 500oC, the reaction between N2 and H2 to form ammonia has
Kc = 6.0x10-2. What is the numerical value of Kp for the reaction?
EXAMPLE
Prediction of the extent of reactions based on
magnitude
High value of Kc or Kp → high concentration of the products
a.) If Kc > 103, the products predominate over the reactants
(the reaction proceeds nearly to completion)
b.) If Kc < 10-3, reactants predominate over the products
(mostly reactants are present in the reaction mixture)
c.) If Kc lies between 10-3 to 103, both reactants and products
are present in appreciable concentration.
EXAMPLE:
Predict the extent of reactions of the following:
1. H2(g) + Cl2(g) ⇌ 2HCl at 300K has Kc = 4.0x1031
2. H2(g) + I2(g) ⇌ 2HI(g) has Kc=57.0
Predicting the Direction of the Reaction
*Qc → reaction quotient at any time
a.) If Qc > Kc, the reaction will proceed in the direction of the reactants
(the reverse reaction will take place)
b.) If Qc < Kc, the reaction will proceed in the direction of the products
(forward reaction will take place)
c.) If Qc = Kc, the reaction is already in equilibrium
EXAMPLE:
The value of Kc for the reaction 2A ⇌ B + C is 2x10-3. At a given time, the concentration of
the reaction mixture is [A]=[B]=[C] = 3x10-4M. In which direction will the reaction proceed?
EXAMPLE
The reaction 2NO (g) + Cl2(g) ⇌ 2NOCl
was studied at 25oC. The partial pressure at equilibrium were found to be
PNOcl =1.2 atm
PNO = 5.0x10-2 atm
PCl2 = 3.0x10-1 atm
Calculate for the Kp for the reaction at 25oC.
CONDITIONS FOR MAXIMUM YIELD
I N I N D U S T R I A L P RO C E S S E S
In the synthesis of ammonia, what optimum conditions of temperature and pressure will secure the
maximum yield of products?
VA N ’ T H O F F I S OT H E R M
may be used to calculate the change in free energy of a reaction in the
standard (ΔG°) from the equilibrium constant and vice-versa
The sign of ΔG° indicates whether the forward or reverse reaction
is spontaneous.
(1) If ΔG° is negative, log K must be positive and the reaction
proceeds spontaneously in the forward reaction.
(2) If ΔG° is positive, log K must be negative and K is less than
one. The reverse reaction is then spontaneous.
(3) If ΔG° = 0, log K = 0 and K = 1. The reaction is at
equilibrium.
EXAMPLE
The standard free energy change for the reaction is +173.1 kJ.
Calculate Kp for the reaction at 25°C.
EXAMPLE
The value of Kp at 298 K for the reaction

is found to be 826.0, partial pressures being measured in


atmospheric units. Calculate ΔG° in calories at 298 K.
T E M P E R AT U R E D E P E N D E N C E O F
E Q U I L I B R I U M C O N S TA N T ( V A N ’ T
H O F F R E AC TI O N I S O C H O R E )
There is appreciable change in the value of equilibrium constant with
change in temperature.
EXAMPLE
The partial pressure of CO2 in the reaction

is 0.773 mmHg at 500°C. Calculate Kp at 600°C for the above


reaction. ΔH of the reaction is 43.2 kcal per mole and does not change
in the given range of temperatures.
S E AT W O R K
1. One mole of PCl5 is heated in a closed two-litre vessel. At equilibrium 40% of the
PCl5 is dissociated. Calculate the equilibrium constant of the reaction.
2. In the reaction:
the conditions for the maximum yield in terms of temperature, pressure, and
presence of catalyst on the basis of Le Chatelier’s principle, are?
3. The equilibrium constant Kp for the reaction

is 1.22 × 10–3 at 298 K and 2.16 at 498 K. Calculate ΔH° for the reaction.
4. The equilibrium constant of a reaction doubles on raising the temperature from
25°C to 35°C. Calculate the AH° for the reaction.

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