Physical Chemistry for Engineers 2 Lecture

Rey Martin G. Estoque

Adamson University
Chemical Engineering Department
 Equilibrium is defined as a state of balance or a
stable situation where opposing forces cancel each
other out and where no changes are occurring.
 An example of equilibrium is in economics when
supply and demand are equal.
 In this chapter, two types of equilibrium will be
discussed in detail: chemical equilibrium and phase
equilibrium
 Condition in the course of a reversible chemical
reaction in which no net change in the amounts of
reactants and products occurs.
 On a macroscopic perspective, it’s as if there is no
reaction occurring.
 On a microscopic perspective, the rate of the
forward reaction is equal to the rate of the
backward reaction. In effect, the concentrations of
both reactants and products ceases to change.
 States that if a dynamic equilibrium is disturbed by
changing the conditions, the position of equilibrium
shifts to counteract the change to reestablish an
equilibrium.
 If a chemical reaction is at equilibrium and
experiences a change in pressure, temperature, or
concentration of products or reactants, the
equilibrium shifts in the opposite direction to offset
the change.
If the amount of one of the components is
increased, the equilibrium will shift towards
the consumption of that component.
If the amount of one of the components is
decreased, the equilibrium will shift towards
the formation of that component.
If the pressure is increased, the reaction
system is compressed, hence the equilibrium
will shift towards the side that has less
gaseous moles.
If the pressure is decreased, the reaction
system will expand, hence the equilibrium will
shift towards the side that has more gaseous
moles.
If the volume is increased, the reaction
system will expand, hence the equilibrium will
shift towards the side that has more gaseous
moles.
If the volume is decreased, the reaction
system is compressed, hence the equilibrium
will shift towards the side that has less
gaseous moles.
For endothermic reactions, heat is a reactant,
while for exothermic reactions, heat is a
product.
Increasing the temperature will make the
equilibrium shift towards the consumption of
heat, while lowering the temperature will
make the equilibrium shift towards the
formation of heat.
Addition of catalyst DOES NOT affect the
direction of the equilibrium.
Catalysts speed up the chemical reaction. It
does not increase the conversion of reactant.
In other words, it does not change the
equilibrium, but only helps achieve it faster.
For the reversible reaction:
𝑁2(𝑔) + 3𝐻2(𝑔) ⇌ 2𝑁𝐻3(𝑔) + 22𝑘𝑐𝑎𝑙
Determine the direction to which the equilibrium will shift if
the following changes occur:
1. Add N2
2. Add H2
3. Add NH3
4. Remove N2
5. Remove H2
For the reversible reaction:
𝑁2(𝑔) + 3𝐻2(𝑔) ⇌ 2𝑁𝐻3(𝑔) + 22𝑘𝑐𝑎𝑙
Determine the direction to which the equilibrium will shift if
the following changes occur:
1. Remove NH3
2. Increase the temperature
3. Decrease the temperature
4. Increase the pressure
5. Decrease the pressure
Equilibrium constants can either be
expressed in terms of concentration (KC)
or partial pressure (KP).
KC and KP can be converted using the
formula:
𝐾𝑝
𝐾𝑐 = ∆𝑛𝑔
(𝑅𝑇)
The equilibrium constant KC for the
reaction:
2𝐴(𝑔) ⇌ 3𝐵(𝑔) + 𝐶(𝑙)
Is 0.0271M at 1100K. Calculate KP at that
temperature in bar.
 (PIChE National Quiz Bowl 2022 Question)
At 800˚C the value of KP for the decomposition
of methane, according to the reaction below is
23atm.
𝐶𝐻4(𝑔) ⇌ 𝐶(𝑠) + 2𝐻2(𝑔)
Initially 4mol of CH4 were present in a 5L
vessel. Calculate the moles of hydrogen present
at equilibrium.
The equilibrium constant KP for the
dehydrogenation of cyclopentene with iodine
varies with temperature according to the
equation:
4844
𝑙𝑜𝑔 𝐾𝑝 , 𝑏𝑎𝑟 = 7.55 −
𝑇, 𝐾
If I2 and C5H8 are initially at 400˚C and at
concentrations of 0.1M, calculate the final
equilibrium concentration of cyclopentene.
 Phase equilibrium is the term used to describe a state
wherein two or more phases co-exist in equilibrium.
 The stability of phases can be predicted by the chemical
potential, in that the most stable form of the substance
will have the minimum chemical potential at the given
temperature and pressure
 Phase equilibrium can be specified as vapor-liquid, liquid-
liquid (for immiscible systems), vapor-solid, and liquid-solid
equilibrium.
 The Clapeyron is used for solid-liquid equilibrium.
∆𝑃 ∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛
=
∆𝑇 𝑇𝑓𝑢𝑠𝑖𝑜𝑛 ∆𝑉
 For vapor-liquid and vapor-solid systems, the Clapeyron
equation is modified into what we call the Clausius-
Clapeyron Equation.
 Assumptions for the derivation are:
1. Vapor is ideal gas
2. Liquid and solid mass/molar volume is very negligible
compared to that of the gas
The normal boiling point of Br2 is 58.8˚C,
and its vapor pressure at 25˚C is 0.315bar.
Estimate the average ΔHVAP in kJ/mol of
Br2 in this temperature range.
The vapor pressure of solid CO2 is
76.7mmHg at -103˚C and its normal
sublimation point is -78.5˚C. What is the
heat of sublimation of CO2 in cal/mol at its
normal sublimation point?
At 90˚C, the vapor pressure of acetic acid
is 293mmHg, and its vapor pressure at
100˚C is 417mmHg. Calculate the normal
boiling point of acetic acid.
Accurate vapor-pressure data for a substance are given in the
table.
a. Estimate the latent heat of vaporization in kJ/mol over
this temperature range.
b. Estimate the boiling point of this substance.
T(˚C) P(torr)
40 55.364
50 92.592
60 149.51
70 233.847
80 355.343
T(˚C) P(torr)
40 55.364
50 92.592
60 149.51
70 233.847
80 355.343
An ice skating rink contains ice at -10˚C.
Calculate the pressure in psi that an ice
skate blade must exert to allow smooth ice
skating at this temperature. Assume that
ΔHF=1440cal/mol, ρL=1g/mL, and
ρice=0.917g/mL.
 If the enthalpy of vaporization is not given, Trouton’s Rule can be
assumed. That is, the entropy of vaporization can range from 85-
88J/mol-K.
 Recall from Module 1 that for latent heat,
∆𝐻𝑡𝑟𝑎𝑛𝑠
∆𝑆𝑡𝑟𝑎𝑛𝑠 =
𝑇𝑡𝑟𝑎𝑛𝑠
 Therefore, assuming Trouton’s Rule is valid, multiplying the normal
boiling point to the chosen value of entropy of vaporization will give
the enthalpy of vaporization.
 Trouton’s Rule tends to fail for highly polar liquids, because the
stronger intermolecular forces results in a lower entropy of
vaporization.
A more specific version of the Trouton’s Rule is the Trouton-
Hildebrand-Everett rule:
𝑅 4.5 + 𝑙𝑛𝑇𝑏 = ∆𝑆𝑣𝑎𝑝
 Similar to the Trouton’s Rule, multiplication of the normal
boiling point to the calculated entropy of vaporization will
yield the enthalpy of vaporization.
 Unlike the Trouton’s Rule, whose entropy of vaporization is
given in a range of values, the Trouton-Hildebrand-Everett
Rule gives a more concrete value of the entropy of
vaporization, hence it is more valid and must be used in
default.
The normal boiling point of diethyl ether is
34.6˚C. Calculate the enthalpy of
vaporization in kJ/mol assuming Trouton-
Hildebrand-Everett rule applies.
The normal boiling point of Br2 is 58.8˚C.
Calculate its vapor pressure at 25˚C in bar.
Physical Chemistry for Engineers 2 Lecture
Rey Martin G. Estoque
Adamson University
Chemical Engineering Department