CHE 195

PROCESS CHEMISTRY

CHAPTER 1
CHEMICAL EQUILIBRIUM

Prepared by: Mohd Shahrul Nizam Bin Salleh

1.1 REVERSIBLE AND NON-REVERSIBLE REACTIONS
•Reversible:
-The reaction that takes place in both the forward and
backward directions.

Ex: Production of gaseous hydrogen iodide

-The products can react with one another under suitable

conditions to give back the reactants.
-It may be noted that for reversible reactions the symbol
is used between the reactants and products
Cont’d
•Non-revesible:
-The chemical reaction in which the products formed
do not combine to give the reactants.

Ex: Potassium chlorate decomposes on heating to

form potassium chloride and oxygen.

-The products cannot combine to form potassium

chlorate.
-The change occurs only in one direction and the
processes go to completion.
1.2 HOMOGENEOUS AND HETEROGENEOUS EQUILIBRIUM

• Homogeneous equilibrium : The equilibrium reactions in which

all the reactants and the products are in the same phase are called
homogeneous equilibrium reactions.
C2H5OH(l) + CH3COOH(l) ↔ CH3COOC2H5(l) + H2O(l)
N2(g) + 3H2(g) ↔ 2NH3(g)
2SO2(g) + O2(g) ↔ 2SO3(g)

• Heterogeneous equilibrium : The equilibrium reactions in which

the reactants and the products are present in different phases are
called heterogeneous equilibrium reactions.
2NaHCO3(s) ↔ Na2CO3(s) + CO2(g) + H2O(g)
1.3 Kc AND Kp EXPRESSIONS
• Kc - Concentration equilibrium expression.
• The concentrations at the equilibrium point are related by a simple
mathematical equation known as an equilibrium expression which is
governed by an equilibrium constant K, at constant temperature.
• For any reaction in solution or a gaseous mixture:
aA + bB + cC ↔tT + uU + wW

Kc = [T]t [U]u [W]w

[A]a [B]b [C]c

• The forward reaction (RHS) are on the top line and the arithmetical product
of the reactant concentrations from the backward reaction (LHS) are on the
bottom line.
• In all cases the product concentrations are raised to the appropriate power
(a, b, c, .. t, u, w, ..) given by the stoichiometric mole ratios of the balanced
equation.
Cont’d
• For heterogeneous equilibrium, K expressions do not normally include
values for solid phases, since their chemical potential cannot change since
the concentration of a solid cannot change.
• The equilibrium constant, Kc is governed by temperature, which is the only
factor that can alter the internal potential energy of the reactants or
products. The 'rule' for the trend in K value change is provided by Le
Chatelier's Principle.
• If the forward reaction is exothermic, Kc (or Kp later) will decrease
in value with increase in temperature.
• If the forward reaction is endothermic, Kc (or Kp) will increase in
value with increase in temperature.
• Changes in pressure or concentration have no effect on a K value
for ideal mixtures of gases/liquids or solutions.
• Application of a catalyst to a reaction also has no effect on a K
value.
 Example
 Given the esterification reaction: ethanoic acid + ethanol  ethyl ethanoate +
water
CH3COOH(l) + CH3CH2OH(l) ↔ CH3COOCH2CH3(l) + H2O(l)

 A mixture of 1.0 mol of ethanoic acid and 1.0 mol of ethanol was left to
reach equilibrium at 25oC.On analysis of the equilibrium mixture it was
found that by titration with standard sodium hydroxide solution 0.333 mol
of the ethanoic acid was left unreacted.Calculate the value of the
equilibrium constant Kc and give its units.

 The reactant-product mole ratios are 1:1 ==> 1:1

 If 0.333 mol ethanoic acid was left unreacted, then 0.667 mol of the acid
had reacted.
 Therefore 0.667 mol of ethanol must also have reacted, leaving 0.333
unreacted.
Cont’d
 If 0.667 of the acid/ethanol reacted, 0.667 mol of  ethyl ethanoate and 0.667
mol of water must be formed.
 The concentrations = mol / volume, but the volume terms cancel each other
out, so substitution in the equilibrium expression can be done in terms of
final numbers of moles reactants and products
 Kc = [CH3COOCH2CH3(l)] [H2O(l)] \
[CH3COOH(l)] [CH3CH2OH(l)]
Kc = 0.667 x 0.667
0.333 x 0.333
= 4.01 (no units)
Example
 12.0g of pure ethanoic acid was mixed with 11.5g of pure ethanol and left to stand for a
week at room temperature (298K/25oC). The mixture was then mixed with deionised
water and made up to 250 cm3 in a calibrated volumetric flask. When a 25.00 cm 3
aliquot of the mixture was titrated with 0.50 mol dm -3 sodium hydroxide solution using
phenolphthalein indicator (colourless ==> 1st permanent pink end-point), 10.60 cm 3 of
the alkali was needed for complete neutralisation.

(i) CH3COOH(l) + CH3CH2OH(l) ↔ CH3COOCH2CH3(l) + H2O(l) (esterification

reaction)
(ii) CH3COOH(l) + NaOH(aq) ↔ CH3COO-Na+(aq) + H2O(l) (neutralisation titration
reaction)

(a) Calculate the moles of ethanoic acid unreacted in the original mixture.
(b) Calculate the moles of ethanoic acid and ethanol in the starting mixture.
(c) Calculate the moles of ethanol left unreacted and the moles of ethyl ethanoate
ester and water formed.
(d) Calculate the equilibrium constant Kc for this esterification.
Cont’d
a) Moles of ethanoic acid unreacted in the original mixture.
 1 mole CH3COOH : 1 mole NaOH from equation (i) above.
 moles = molarity x vol(dm3), so moles acid = 0.50 x 10.6/1000 = 0.0053 mol
 since the 25.00 cm3 aliquot titrated is equal to 1/10th of the total mixture,
 the total moles of unreacted acid = 10 x 0.0053 = 0.053 mol CH3COOH left

b) Moles of ethanoic acid and ethanol in the starting mixture.

 Mr(CH3COOH) = 60, mol ethanoic acid = 12/60 = 0.20
 Mr(CH3CH2OH) = 46, mol ethanol = 11.5/46 = 0.25

c) Moles of ethanol left unreacted and the moles of ethyl ethanoate ester and water formed.

equation CH3COOH(l) + CH3CH2OH(l) ↔ CH3COOCH2CH3(l) + H2O(l)

moles at start 0.20                 0.25                    0                             0
mol at equilibrium 0.20 - x            0.25 - x               x                             x
mol at equilibrium 0.053         0.103            0.147              0.147
Cont’d
 x = moles of ester or water formed,
 so x mol of acid or alcohol must be used to reach equilibrium,
 since mol ratios are 1:1 ==> 1:1 in the reaction equation.
 Therefore 0.20 - x = 0.053 from calculation (a), therefore x = 0.20 - 0.053 = 0.147
 so all the molar quantities can be logically deduced and are shown in the final line
of the table.

c) Equilibrium constant Kc for this esterification.

Kc = [CH3COOCH2CH3(l)] [H2O(l)]
[CH3COOH(l)] [CH3CH2OH(l)]
Kc = (0.147/V) x (0.147/V)
(0.053/V) x (0.103/V)
= 3.96 (no units)

Note that all the volume terms cancel out, so you can work purely in moles to calculate
Kc .
Kp Expression
• Kp - Partial equilibrium expression.
• For any gaseous reaction:
aA (g)+ bB(g) + cC(g) ↔tT(g) + uU(g) + wW(g)

Kp = pTt pUu pww.

pAa pBb pCc
• px indicates the partial pressure of x, usually in atm (atmospheres) or Pa
(pascals).
• The partial pressure of a gas is defined as the pressure a gaseous component
in a mixture would exert, if it alone occupied the space/volume in question.
• e.g. in air, 21% by volume is oxygen and 79% is nitrogen etc.
• Therefore the fraction of molecules which are oxygen and nitrogen is 0.21
and 0.79 respectively.
Cont’d
• Since air has a total pressure of 1 atm. or 101325 Pa, the partial pressures of
oxygen and nitrogen in air are:
• pO2 = 0.21 x 1 = 0.21 atm or pO2 = 0.21 x 101325 = 21278 Pa,
• pN2 = 0.79 x 1 = 0.79 atm or pN2 = 0.79 x 101325 = 80047 Pa,
• In other words, the partial pressure of a gas in a mixture pgas = its % x ptot /
100
• In a gaseous mixture the total pressure equals the sum of all the partial
pressures:
• ptot = p1 + p2 + p3 etc.
• so for air : ptot-air = pO2 + pN2 + pAr + pCO2. = 1 atm or 101325 Pa
• The % by volume ratio is also the mole ratio of the gases in a mixture.
• If we call x the mole fraction of gas in a mixture then:
• The mole fraction of a gas A in a mixture = xA = mol of A / total moles of
all gases
• Therefore the partial pressure of gas A, pA = xA x ptot
Example
• 2SO2(g) + O2(g) ↔ 2SO3(g) (sulphur trioxide)

Kp = pSO32 (units atm-1 or Pa-1)

pSO22 pO2

• Ammonia is synthesised by combing nitrogen and hydrogen, but the reaction is

reversible.
N2(g) + 3H2(g) ↔ 2NH3(g) (ΔH = -92 kJ mol-1)
• In an experiment starting with a 1:3 ratio H2:N2 mixture, at 400oC and total
pressure of 200 atm, the equilibrium mixture was found to contain 36.3% by
volume of ammonia.
(a) Write out the equilibrium expression for Kp.
(b) Calculate the partial pressures of nitrogen, hydrogen and ammonia.
(c) Calculate the value of the equilibrium constant at 400oC and give its units.
Cont’d
a) Kp = pNH32 (units atm-2 or Pa-2)
pN2 pH23

b) Partial pressures of nitrogen, hydrogen and ammonia.

 36% of ammonia means its mole fraction is 0.36, so pNH3 = 0.36 x 200 = 72
atm
 The other 64% of gases must be split on a 1:3 ratio between nitrogen and
hydrogen.
 If you think of the 1:3 ratio as 1 and 3 parts out of 4 the logic becomes easy.
 So mole fraction of nitrogen x ptot = pN2 = 64/100 x 1/4 x 200 = 32 atm,
and mole fraction of hydrogen x ptot = pH2 = 64/100 x 3/4 x 200 = 96 atm
check: ptot = pN2 + pH2 + pNH3 = 32 + 96 + 72 = 200 atm!
 Cont’d
c) Value of the equilibrium constant at 400oC.
Kp = pNH32
= pN2 pH23
Kp = 722
32 x 963
= 1.83 x 10-4 atm-2

Converting Kc to Kp.
2NOCl(g) ↔ 2NO(g) + Cl2(g)
Kc = 3.75 x 10-6 at 796oC.
 Write the expression to convert
Kc to Kp: KP = Kc(RT)Δn
 Extract the relevant data from the question:
R = 0.0821 (Ideal Gas Constant)
T = 796oC = 796 + 273 = 1069K
Δn = (2 + 1) - 2 = 1 (moles of gaseous product –moles of gaseous reactant
 KP = Kc(RT)Δn
KP = 3.75 x 10-6(0.0821 x 1069)1
REACTION QUOTIENT (QC)
EQUILIBRIUM CONSTANT (KC)

What is the difference ?

The concentration in the Qc can be
any concentration (usually initial
concentration)
but

The concentration in the Kc expression

must be at equilibrium concentration
 Comparison the value of
Reaction quotient (Qc)
and Equilibrium constant (Kc)

To determine the direction in which

the net reaction will proceed to
achieve equilibrium
 The reaction quotient (Qc) is calculated by substituting the
initial concentrations of the reactants and products into the
equilibrium constant (Kc) expression.
IF
• Qc > Kc system proceeds from right to left to reach equilibrium
• Qc = Kc the system is at equilibrium
• Qc < Kc system proceeds from left to right to reach equilibrium
1.4 Le Chatelier’s Principle
• Le Chateliers's Principle states that if an 'instantaneous' change is imposed on
an equilibrium, the position of the equilibrium will further change to minimise
the 'enforced' change.
• So the system reaches a new equilibrium position
• In other words, if a change is 'instantaneously' imposed, the equilibrium
attempts to restore the original situation, but it cannot do this completely BUT
the change 'trend' can be predicted.
• Le Chatelier’s Principles
 Temperature and energy changes (ΔH)
 Raising the temperature favours the endothermic direction (ΔH +ve). The
system absorbs the heat energy from the surroundings to try to minimise the
temperature increase
 Decreasing the temperature favours the exothermic direction (ΔH -ve). The
system releases heat energy to the surroundings to try to minimise the
temperature decrease.
Cont’d
 Gas pressure changes at constant temperature (ΔV)
 Increasing the pressure favours the side of the equilibrium with the least
number of gaseous molecules as indicated by the balanced symbol
equation. The system attempts to reduce the number of gas molecules
present to reduce the pressure increase.
 Decreasing the pressure favours the side of the equilibrium with the most
number of gaseous molecules as indicated by the balanced symbol
equation. The system attempts to increase the number of gas molecules to
minimise the pressure decrease
 Concentration changes at constant temperature
 If the concentration of a reactant (on the left) is increased, then some of it
must change to the products (on the right) to maintain a balanced
equilibrium position.
 If the concentration of a reactant (on the left) is decreased, then some of 
the products (on the right) must change back to reactants to maintain a
balanced equilibrium position.
Cont’d
 Using a catalyst
 A catalyst does NOT affect the position of an equilibrium.
 BUT it does is enable you get to the point of equilibrium faster
 !A catalyst speeds up both the forward and reverse reactions by
providing a mechanistic pathway with a lower activation energy, but
there is no way it can influence the final 'balanced' concentration ratios.
 The importance of a catalyst lies with economics of chemical
production
 e.g. bringing about reactions with high activation energies at lower
temperatures and so reducing energy requirements and time, and both
reductions save money!
 Example
Changes in Concentration.
Consider the following system at equilibrium:

Fe3+(aq) + SCN-(aq) ↔ FeSCN2+(aq)

(colourless) (red)

- Increasing the concentration of either Fe3+(aq) or SCN-(aq) will result in the

equilibrium position moving to the right, using up the some of the additional
reactants and producing more FeSCN2+(aq).
The solution will become a darker red colour.
- Removing some of the Fe3+(aq) or SCN-(aq) will result in the equilibrium position
moving to the left to produce more Fe3+(aq) and SCN-(aq).
The solution will become less red as FeSCN2+(aq) is consumed.
PRACTICE EXERCISE
 Predict the direction of equilibrium position when the pressure is
increase. Why?
2NO2(g) ↔ N2O4(g)
(red-brown) (colourless)

 What happens to the Products if:

a. More Reactanct are added to the system? explain why
b. temperature is decreased? explain why
c. pressure is decreased? explain why
PRACTICE EXERCISE
 A closed system initially containing 1.000 x 10−3 M H2 and 2.000 x
10−3 M I2 at 448°C is allowed to reach equilibrium. Analysis of the
equilibrium mixture shows that the concentration of HI is 1.87 x
10−3 M. Calculate Kc at 448°C for the reaction
H2 (g) + I2 (g) ↔ 2 HI (g)