General Chemistry#9

For Chemical Engineering

Chemical Reaction Equilibrium

1
 Chemical Equilibrium
• What is equilibrium?
• Expressions for equilibrium constants, Kc;
• Calculating Kc using equilibrium concentrations;
• Calculating equilibrium concentrations using initial 
concentration and Kc value;
• Relationship between Kc and Kp;
• Factors that affect equilibrium;
• Le Chatelier’s Principle
What is Equilibrium?
This is not Equilibrium?
 Chemical Equilibrium in Nature:
(The formation of stalagmites and Stalactites)

Formation of stalactites and stalagmites

CaCO3(s) + H2O(liq) + CO2(g) Ca2+(aq) + 2 HCO3-(aq)
 The Concept of Equilibrium

Chemical equilibrium occurs when a

reaction and its reverse reaction proceed at
the same rate.
The Concept of Equilibrium
• As a system
approaches equilibrium,
both the forward and
reverse reactions are
occurring.
• At equilibrium, the
forward and reverse
reactions are
proceeding at the same
rate.
 A System at Equilibrium

Once equilibrium is
achieved, the
amount of each
reactant and product
remains constant.
 A System at Equilibrium
Rates become equal Concentrations become constant
 Depicting Equilibrium

In a system at equilibrium, both the

forward and reverse reactions are
running simultaneously. We write the
chemical equation with a double arrow:
 Chemical Equilibrium
• Consider the following reactions:
CaCO3(s) + CO2(aq) + H2O(l)  Ca2+(aq) + 2HCO3­(aq) ..(1)
and
Ca2+(aq) + 2HCO3­(aq)  CaCO3(s) + CO2(aq) + H2O(l) ..(2)

Reaction (2) is the reverse of reaction (1). 
At equilibrium the two opposing reactions occur at the 
same rate. 
Concentrations of chemical species do not change once 
equilibrium is established.
The Equilibrium
Constant
 Expression for Equilibrium Constant

Consider the following equilibrium system:
wA +  xB  ⇄  yC  +  zD

Kc =

• The numerical value of Kc is calculated using the 
concentrations of reactants and products that exist at 
equilibrium.
 Expressions for Equilibrium Constants

• Examples:
[NH 3 ] 2
N2(g)  +  3H2(g)  ⇄  2NH3(g);   Kc =  [N 2 ][H 2 ]3

[PCl 3 ][Cl 2 ]
PCl5(g) ⇄  PCl3(g) +  Cl2(g);     Kc =   [PCl 5 ]

CH4(g)  + H2(g) ⇄  CO(g)  +  3H2(g);
[CO][H 2 ]3
 Kc =  [CH 4 ][H 2 O]
Equilibrium Can Be Reached from Either
Direction

Kc, the final ratio of [NO2]2 to [N2O4], reaches a

constant no matter what the initial concentrations
of NO2 and N2O4 are (with const T).
Equilibrium Can Be Reached from
Either Direction
This graph shows data
from the last two trials
from the table.
Equilibrium Can Be Reached from Either
Direction

It does not matter whether we start with N2 and H2 or

whether we start with NH3. We will have the same
proportions of all three substances at equilibrium.
What is the equilibrium expression?
What Does the Value of K Mean?
• If K >> 1, the reaction
is product-favored;
product predominates
at equilibrium.
What Does the Value of K Mean?
• If K >> 1, the reaction
is product-favored;
product predominates
at equilibrium.

• If K << 1, the reaction is

reactant-favored;
reactant predominates
at equilibrium.
Manipulating Equilibrium Constants
The equilibrium constant of a reaction in the
reverse reaction is the reciprocal of the
equilibrium constant of the forward reaction.
Manipulating Equilibrium Constants
The equilibrium constant of a reaction that has been
multiplied by a number is the equilibrium constant
raised to a power that is equal to that number.
Manipulating Equilibrium Constants
The equilibrium constant for a net reaction made up
of two or more steps can be found from the
equilibrium constants for the individual steps.`
At 1565 K we have these equilibrium constants:

ans= 0,350823
 Calculating Equilibrium Constant

• Example-1:
1.000 mole of H2 gas and 1.000 mole of I2 vapor are
introduced into a 5.00-liter sealed flask. The mixture is
heated to a certain temperature and the following reaction
occurs until equilibrium is established.
H2(g) + I2(g) ⇄ 2HI(g)
At equilibrium, the mixture is found to contain 1.580 mole
of HI. (a) What are the concentrations of H2, I2 and HI at
equilibrium? (b) Calculate the equilibrium constant Kc.
 Calculating Equilibrium Constant
for reaction:  H2(g)  +  I2(g)  ⇄  2HI(g)
• ————————————————————————————
• H2(g)    +    I2(g)     ⇄      2 HI(g)
• ————————————————————————————
• Initial [  ], M: 0.200           0.200           0.000
• Change in [  ], M:    ­0.158             ­0.158        + 0.316
• Equilibrium [  ], M 0.042              0.042           0.316
• ————————————————————————————

[HI]2 (0.316) 2
[H 2 ][I 2 ] (0.042) 2
Kc =     =   =  57
 Calculating Equilibrium Constant

• Example-2:
0.500 mole of HI is introduced into a 1.00 liter sealed flask
and heated to a certain temperature. Under this condition
HI decomposes to produce H2 and I2 until an equilibrium is
established. An analysis of the equilibrium mixture shows
that 0.105 mole of HI has decomposed. Calculate the
equilibrium concentrations of H2, I2 and HI, and the
equilibrium constant Kc for the following reaction:
        H2(g)  +  I2(g)  ⇄  2HI(g),
 Calculating Equilibrium Constant

• The reaction:  H2(g)  +  I2(g)  ⇄  2HI(g),  proceeds from 
right to left.
• ————————————————————————————
•  H2(g)  +     I2(g)   ⇄    2HI(g)
• ————————————————————————————
• Initial [  ], M: 0.000         0.000              0.500
• Change in [  ], M:   +0.0525         +0.0525           ­0.105
• Equil’m [  ], M 0.0525         0.0525            0.395
• ————————————————————————————
2
(0.395)
(0.0525) 2
Kc  =                          = 56.6
 Expression and Value of 
Equilibrium Constant for a Reaction
• The expression for K depends on the equation;
• The value of K applies to that equation; it does 
not depend on how the reaction occurs;
• Concentrations used to calculate the value of K 
are those measured at equilibrium.
 Relationships between chemical equations and 
the expressions of equilibrium constants
• The expression of equilibrium constant depends on how the
equilibrium equation is written. For example, for the
following equilibrium: 2
[HI]
• H2(g) + I2(g) ⇄ 2 HI(g); Kc 
[H 2 ][I 2 ]
• For the reverse reaction:
[H 2 ][I 2 ]
• 2HI(g) ⇄ H2(g) + I2(g); K c '  2
1/K c
[HI]
• And for the reaction: HI(g) ⇄ ½H2(g) + ½I2(g);

[H 2 ][ I 2 ] 1
Kc "   K c ' 
[HI]2 Kc
 The Equilibrium Constant
Because pressure is proportional to
concentration for gases, the equilibrium
expression can also be written in terms of
partial pressures (instead of concentration):

Mixed versions are also used sometimes:

Relationship between Kc and Kp
• From the ideal gas law we know that

= Pressure in terms of concentration

 Relationship between Kc and Kp
Substituting P=[A]RT into the expression for
Kp for each substance, the relationship
between Kc and Kp becomes

Kp = Kc (RT)n
Where:
n = (moles of gaseous product) – (moles of gaseous reactant)

Hint: ‘products–reactants’ and ‘products over reactants’

is a common theme in chemistry.
 Expression and Values of
Equilibrium Constant Using Partial Pressures

• Consider the following reaction involving 
gases:
2SO2(g)  +  O2(g) ⇄ 2SO3(g)
(PSO3 ) 2
      Kp = (P ) 2 (P )
SO2 O2
 The Relationship between Kc and Kp

• Consider the reaction: 2SO2(g) + O2(g) ⇄ 2SO3(g)

[SO]2 (PSO3 ) 2
• Kc = and Kp =
[SO 2 ]2 [O 2 ] (PSO2 ) 2 (PO2 )
• Assuming ideal behavior,
• where PV = nRT and P = (n/V)RT = [M]RT
• and PSO3 = [SO3]RT; PSO2 = [SO2]RT; PO2 = [O2]RT
[SO 3 ]2 ( RT) 2 [SO 3 ]2 -1 -1
Kp  2 2
 2
( RT) K c ( RT)
[SO 2 ] ( RT) [O 2 ]( RT) [SO 2 ] [O 2 ]
 Relationship between Kc and Kp

• For reaction: PCl5(g)  PCl3(g) + Cl2(g);

(PPCl3 )( PCl2 ) [PCl 3 ]( RT) x [Cl 2 ]( RT)

Kp  
( PPCl5 ) [PCl 5 ]( RT)
[PCl 3 ][Cl 2 ]
 ( RT) 1  K C ( RT) 1
[ PCl 5 ]
 Relationship between Kc and Kp
• In general, for reactions involving gases such that,

• aA + bB ⇄ cC + dD
where A, B, C, and D are all gases, and a, b, c,
and d are their respective coefficients,
• Kp = Kc(RT)n
and n = (c + d) – (a + b)
(In heterogeneous systems, only the coefficients
of the gaseous species are counted.)
 Relationship between Kc and Kp
• For other reactions:
• 1. 2NO2(g) ⇄ N2O4(g); Kp = Kc(RT)-1
• 2. H2(g) + I2(g) ⇄ 2 HI(g); Kp = Kc
• 3. N2(g) + 3H2(g) ⇄ 2 NH3(g); Kp = Kc(RT)-2
 Homogeneous & Heterogeneous Equilibria

Homogeneous equilibria:
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g);
CO(g)  +  H2O(g) ⇄ CO2(g) + H2(g);

Heterogeneous equilibria:
CaCO3(s) ⇄  CaO(s)  +  CO2(g);
HF(aq) + H2O(l) ⇄ H3O+(aq) + F­(aq);
PbCl2(s) ⇄ Pb2+(aq) + 2 Cl­(aq);
 Equilibrium Constant Expressions for 
Heterogeneous System
• Examples:
CaCO3(s) ⇄  CaO(s)  +  CO2(g);
Kc = [CO2]     Kp = PCO2;    Kp = Kc(RT)

• HF(aq) + H2O(l) ⇄ H3O+(aq)  + F­(aq);
[H 3O  ][ F - ]
Ka 
[HF]
 Solubility Eqilibrium

PbCl2(s) ⇄  Pb2+(aq)  +  2Cl­(aq);  
Ksp = [Pb2+][Cl­]2

(Ksp is called solubility product)
Combining Equations and Equilibrium Constants

• when two or more equations are added to yield a net

equation, the equilibrium constant for the net
equation, Knet, is equal to the product of equilibrium
constants of individual equations.
• For example,
[C][D]
Eqn(1): A + B ⇄ C + D; K1 
[A][D]

[B][F]
Eqn(2): C + E ⇄ B + F; K2 
[C][E]
Combining Equations and Equilibrium Constants

• Net equation: A + E ⇄ D + F;

[D][F]
K net 
[A][E]
= K1 x K2

• If Eqn(1) + Eqn(2) = Net equation,

then K1 x K2 = Knet
 Entropy
We all know that heat flow from a high-T object into a low-T object. This type
of change can be described as due to increase of entropy.
Entropy S is the amount of energy transferred, E, divided by T.
E
S = ———— or TS = E
T
Entropy increases for spontaneous changes (reactions).
Entropy is also associated with randomness of ordering.

What causes change when no apparent energy is involved?

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 Entropy calculation
A system consists 10.0 L of water at 300 K and 3.0 g of ice at 273 K. Heat
of fusion of ice (molar mass 18) is 6 kJ/mol. What is the change in entropy
when the system is at equilibrium.
Solution:
Since the amount of heat for melting the ice is
6 *(3/ 18) = 1.0 kJ
too little to change the temperature of the entire system appreciably from 300
K. Thus the entropy change is
– 1/300 + 1/273 = 3.3e – 4 kJ/K = 0.33 J/K (entropy unit)
What is the molar entropy for ice melting?
+6000 J mol–1 / 273 K = 22 J mol –1 K –1 (entropy unit mol–1)

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 Josiah W. Gibbs
(1839-1903) New Haven, Connecticut, USA
First Doctorate (1863 Yale) in Engineering of U.S.A.
Studied in Europe, influenced by Kirchhoff & Helmholtz.
1871 Professor of mathematics and physics at Yale

Unassuming in manner, genial and kindly in his intercourse with his fellow-men,
never showing impatience or irritation, devoid of personal ambition of the baser sort
or of the slightest desire to exalt himself, he went far toward realizing the ideal of the
unselfish, Christian gentleman. In the minds of those who knew him, the greatness
of his intellectual achievements will never overshadow the beauty and dignity of his
life. - Bumstead

lunar crater Gibbs 44

 Gibbs free energy, G or G
Following the definition of entropy S, Gibbs defined a function together with
enthalpy of change, H.
G=H–TS now called Gibbs free energy.
or G = H – T S for differences of these quantities
Since H is negative and S is positive for spontaneous change, Gibbs free
energy is negative for all spontaneous changes, and it unified enthalpy and
entropy for changes. Gibbs free energy is the maximum amount of available
energy in any change.
Similar to Ho, Go is the Gibbs free energy at the standard T and P.

What drives physical and chemical changes?

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 Energy and equilibrium constant K
A quantity called Gibbs free energy, G, is defined as the maximum
amount of energy from a chemical reaction for doing work.
G is negative for spontaneous reaction
G is positive for non-spontaneous reaction
The G is related to the reaction quotient Q,
G = Go + R T ln Q
When a system is at equilibrium there is no available energy,
G = Go + R T ln K = 0
Thus,
Go = – R T ln K, ln K = – Go / R T
K = exp (– Go / R T)

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More expressions for equilibrium constant
Note these relationships in light of ln K = – Go / R T

[H2O]2
2 H2 + O2  2 H2O K = —————
[H2]2 [O2]

[H2]2 [O2] 1
K r = ———— = —— 2 H2O  2 H2 + O2
[H2O] 2 K

[H2O]4
4 H2 + 2 O2  4 H2O K2 = ————— = K 2
[H2]4 [O2]2

K2=K

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 Equilibrium Exercise #1
A flask is charged with 2.00 atm of nitrogen dioxide and
1.00 atm of dinitrogen tetroxide at 25 oC and allowed to
reach equilibrium. When equilibrium is established, the
partial pressure of NO2 has decreased by 1.24 atm. (a) What
are the partial pressures of NO2 and N2O4 at equilibrium?
(b) Calculate Kp and Kc for following reaction at 25 oC.
2 NO2(g) ⇄ N2O4(g)

(Answer: Kp = 2.80; Kc = 68.6)

 Equilibrium Exercise #2a
• Methanol is produced according to the following equation:
• CO(g) + 2H2(g) ⇄ CH3OH(g)
• In an experiment, 1.000 mol each of CO and H2 were allowed
to react in a sealed 10.0-L reaction vessel at 500 K. When the
equilibrium was established, the mixture was found to contain
0.0892 mole of CH3OH. What are the equilibrium
concentrations of CO, H2 and CH3OH? Calculate the
equilibrium constants Kc and Kp for this reaction at 500 K?
(R = 0.0821 L.atm/Mol.K)

(Answer: [CO] = 0.0911 M; [H2] = 0.0822 M; [CH3OH] = 0.00892 M;

(b) Kc = 14.5; Kp = 8.60 x 10-3)
 Equilibrium Exercise #2b
For the reaction: CO(g) + 2H2(g) ⇄ CH3OH(g)
Kc = 15.0 at a certain temperature. Is a reaction
mixture that contains 0.40 M CO, 0.80 M H2, and
0.10 M CH3OH at equilibrium? If not, in which
direction will the net reaction occur? What will be
their concentrations when equilibrium is established?
 Equilibrium Exercise #3

1. The reaction: N2(g) + 3H2(g) ⇄ 2NH3(g),

has equilibrium constant, Kc = 0.0602 at 500oC.
What is the equilibrium constant for the following reaction?
NH3(g) ⇄ ½N2(g) + 3/2H2(g)

2. For the reaction: 2SO2(g) + O2(g) ⇄ 2 SO3(g),

Kc = 280 at 1000 K.
What is the equilibrium constant for the decomposition of
SO3 at 1000 K according to the following equation?
SO3(g) ⇄ SO2(g) + ½ O2(g).
 Equilibrium Exercise #4

If N2(g) + ½ O2(g) ⇄ N2O(g); Kc(1) = 2.4 x 10-18

and N2(g) + O2(g) ⇄ 2 NO(g); Kc(2) = 4.1 x 10-31
What is the equilibrium constant for the reaction?
N2O(g) + ½ O2(g) ⇄ 2NO(g)

(Answer: Knet = 1.7 x 10-13)

 Applications of Equilibrium Constant

For any system or reaction:
1. Knowing the equilibrium constant, we can predict 
whether or not a reaction mixture is at 
equilibrium, and we can predict the direction of 
net reaction.
• Qc = Kc  equilibrium (no net reaction)
• Qc < Kc  a net forward reaction; 
• Qc > Kc  a net reverse reaction
2. The value of K tells us whether a reaction favors 
the products or the reactants.
 Equilibrium constant is used to predict the
direction of net reaction
• For a reaction of known Kc value, the direction of net reaction
can be predicted by calculating the reaction quotient, Qc.
• Qc is called the reaction quotient, where for a reaction such
as: c d
[C] [ D]
• aA + bB ⇄ cC + dD; Qc 
[A]a [ B]b
• Qc has the same expression as Kc , but
• Qc is calculated using concentrations that are not necessarily at
equilibrium.
What does the reaction quotient tell us?
If Qc = Kc,  the reaction is at equilibrium;
If Qc < Kc,  the reaction is not at equilibrium and there’s a
net forward reaction;
If Qc > Kc,  the reaction is not at equilibrium and there’s a
net reaction in the opposite direction.
 Why is Equilibrium Constant Important?

• Knowing Kc and the initial concentrations, we can 
determine the concentrations of components at 
equilibrium.
 Equilibrium Exercise #5

• For the reaction:

CO(g) + 2 H2(g) ⇄ CH3OH(g), Kc = 14.5 at 500 K.
• Predict whether a mixture that contains 1.50 mol of H 2, 1.00
mol of CO, and 0.50 mol of CH3OH in a 10.0-L vessel at
500 K is at equilibrium.
• If not, indicate the direction in which the net reaction will
occur to reach equilibrium.

(Answer: Qc = 22.2 > Kc; net reaction is to the left)

 Calculating equilibrium concentrations using
initial concentrations and value of Kc

• Consider the reaction:

• H2(g) + I2(g) ⇄ 2 HI(g),
• where Kc = 55.6 at 425oC.
• If [H2]0 = [I2]0 = 0.1000 M, and [HI]0 = 0.0 M, what
are their concentrations at equilibrium?
 Using the ICE table to calculate
equilibrium concentrations
• Equation: H2(g) + I2(g) ⇄ 2 HI(g),
 

• Initial [ ], M 0.1000 0.1000 0.0000

• Change [ ], M -x -x +2x
• Equilibrium [ ], M (0.1000 - x) (0.1000 - x) 2x
  

[HI]2 (2 x ) 2
Kc   2
55.6
[H 2 ][ I 2 ] (0.100 - x )
Calculation of equilibrium concentrations

2x
 55.6 7.46
(0.100 - x
2 x 0.746 - 7.46 x; 9.46 x 0.746
x 0.0789 ;
[H 2 ] [I 2 ] 0.0211 M; [HI] 0.158 M
 Equilibrium Exercise #6

For the reaction:

2 NO2(g) ⇄ N2O4(g); Kp = 1.27 at 353 K.
If the initial pressure of NO2 was 3.92 atm, and
initially there was no N2O4, what are the partial
pressures of the gases at equilibrium at 353 K?
What is the total gas pressure at equilibrium?

(Answer: PNO2 = 1.06 atm; PN2O4 = 1.43 atm; Ptotal = 2.49 atm)
 Equilibrium Exercise #7
The reaction:
PCl5(g) ⇄ PCl3(g) + Cl2(g) has Kc = 0.0900.
A 0.1000-mol sample of PCl5 is placed in an empty
1.00-L flask and the above reaction is allowed to
come to equilibrium at a certain temperature. How
many moles of PCl5, PCl3, and Cl2, respectively, are
present at equilibrium?

(Answer: PCl5 = 0.0400 mol; PCl3 = Cl2 = 0.0600 mol)

 Le Châtelier’s Principle
• The Le Châtelier's principle states that:
when factors that influence an equilibrium are altered, the
equilibrium will shift to a new position that tends to
minimize those changes.

• Factors that influence equilibrium:

Concentration, temperature, and partial pressure (for
gaseous)
 The Effect of Changes in Concentration

• Consider the reaction: N2(g) + 3H2(g) ⇄ 2 NH3(g);

[NH 3 ]2
Kc 
[N 2 ][H 2 ]3
• If [N2] and/or [H2] is increased, Qc < Kc
 a net forward reaction will occur to reach new equilibrium
position.
• If [NH3] is increased, Qc > Kc, and a net reverse reaction
will occur to come to new equilibrium position.
Effects of Pressure Change on Equilibrium

• If the volume of a gas mixture is compressed, the

overall gas pressure will increase. In which direction
the equilibrium will shift in either direction depends
on the reaction stoichiometry.

• However, there will be no effect to equilibrium if the

total gas pressure is increased by adding an inert gas
that is not part of the equilibrium system.
Reactions that shift right when pressure increases
and shift left when pressure decreases
Consider the reaction:
2SO2(g) + O2(g) ⇄ 2SO3(g),
1. The total moles of gas decreases as reaction
proceeds in the forward direction.
2. If pressure is increased by decreasing the volume
(compression), a forward reaction occurs to reduce
the stress.
3. Reactions that result in fewer moles of gas favor
high pressure conditions.
Reaction that shifts left when pressure increases,
but shifts right when pressure decreases

Consider the reaction: PCl5(g) ⇄ PCl3(g) + Cl2(g);

1. Forward reaction results in more gas molecules.

2. Pressure increases as reaction proceeds towards
equilibrium.
3. If mixture is compressed, pressure increases, and
reverse reaction occurs to reduce pressure;
4. If volume expands and pressure drops, forward
reaction occurs to compensate.
5. This type of reactions favors low pressure condition
Reactions not affected by pressure changes

Consider the following reactions:

1. CO(g) + H2O(g) ⇄ CO2(g) + H2(g);
2. H2(g) + Cl2(g) ⇄ 2HCl(g);
1. Reactions have same number of gas molecules in
reactants and products.
2. Reducing or increasing the volume will cause equal
effect on both sides – no net reaction will occur.
3. Equilibrium is not affected by change in pressure.
 The Effect Temperature on Equilibrium
• Consider the following exothermic reaction:
N2(g) + 3H2(g) ⇄ 2NH3(g); Ho = -92 kJ,
• The forward reaction produces heat => heat is a product.
• When heat is added to increase temperature, reverse reaction
will take place to absorb the heat;
• If heat is removed to reduce temperature, a net forward
reaction will occur to produce heat.
• Exothermic reactions favor low temperature conditions.
 The Effect Temperature on Equilibrium

Consider the following endothermic reaction:

CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g), Ho = 205 kJ
1. Endothermic reaction absorbs heat  heat is a reactant;
2. If heat is added to increasing the temperature, it will cause a
net forward reaction.
3. If heat is removed to reduce the temperature, it will cause a
net reverse reaction.
4. Endothermic reactions favor high temperature condition.
 Equilibrium Exercise #8

Determine whether the following reactions favor

high or low pressures?
1. 2SO2(g) + O2(g) ⇄ 2 SO3(g);
2. PCl5(g) ⇄ PCl3(g) + Cl2(g);
3. CO(g) + 2H2(g) ⇄ CH3OH(g);
4. N2O4(g) ⇄ 2 NO2(g);
5. H2(g) + F2(g) ⇄ 2 HF(g);
 Equilibrium Exercise #9

• Determine whether the following reactions favors

high or low temperature?

1. 2SO2(g) + O2(g) ⇄ 2 SO3(g); Ho = -180 kJ

2. CO(g) + H2O(g) ⇄ CO2(g) + H2(g); Ho = -46 kJ
3. CO(g) + Cl2(g) ⇄ COCl2(g); Ho = -108 kJ
4. N2O4(g) ⇄ 2 NO2(g); Ho = +57 kJ
5. CO(g) + 2H2(g) ⇄ CH3OH(g); Ho = -270 kJ
 Chemical Equilibria in Industrial Processes
Production of Sulfuric Acid, H2SO4;
1. S8(s) + 8 O2(g)  8SO2(g)
2. 2SO2(g) + O2(g) ⇄ 2SO3(g); H = -198 kJ
3. SO3(g) + H2SO4(l)  H2S2O7(l)
4. H2S2O7(l) + H2O(l)  2H2SO4(l)

• The second reaction is exothermic and has high activation

energy;
• though thermodynamically favored the reaction is very slow
at low temperature,.
• At high temperature reaction goes faster, but the yield would
be very low.
• An optimum condition is achieved at moderate temperatures
and using catalysts to speed up the reaction. Reaction also
favors high pressure.
 Chemical Equilibria in Industrial Processes

The production of ammonia by the Haber-Bosch

process:
N2(g) + 3H2(g) ⇄ 2NH3(g); H = -92 kJ

• This reaction is exothermic and very slow at low temperature.

• Increasing the temperature will increase reaction rate, but will
lower the yield.
• An optimum condition is achieved at moderate temperature of
250 to 300oC with catalyst added to increase the reaction rate.
• Increasing the pressure will favor product formation.
• Reaction favors low temperature and high pressure conditions.
 Chemical Equilibria in Industrial Processes

The production of hydrogen gas:

• Reaction: CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g);
• This reaction is endothermic with H = 206 kJ
• Increasing the reaction temperature will increase both
the rate and the yield.
• This reaction favors high temperature and low
pressure conditions.