UNIVERSITY OF SANTO TOMAS

CHEMICAL ENGINEERING SOCIETY

CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS

CHE216: Physical Chemistry for Engineers 1

PHYSICAL CHEMISTRY

Chemistry + Physics

The key concepts of physical chemistry are the ways in

which pure physics is applied to chemical problems.

Physical chemistry, in contrast to chemical physics, is

predominantly (but not always) a macroscopic or supra-
molecular science, as the majority of the principles on
which it was founded relate to the bulk rather than the
molecular/atomic structure alone.

CHAPTER 1: THE PROPERTIES OF GASES

1A The perfect gas

Mechanical Equilibrium- condition of equality of
Gas - a collection of molecules pressure on either side of a movable wall
-in ceaseless motion
- collides significantly when they collide
Standard Pressure
1A.1 Variables of state o STP: 1 atm (101.325 KPa)
 Pressure (P) o SATP: 1 bar (100 KPa)
 Temperature (T)
 Volume (V)
 Amount of substance (n) *STP- Standard Temperature and Pressure
*SATP- Standard Ambient Temperature and Pressure
a. Pressure Example Problem 1: 5 mins
Derive an equation for the pressure at the base
-Steady force exerted by numerous gas of a column of liquid of mass density ρ (rho) and
molecule collisions (F/A) height h at the surface of the Earth. The
A gas that has higher pressure will tend to pressure exerted by a column of liquid is
compress the gas of lower pressure. commonly called the ‘hydrostatic pressure’.

Clue: Pressure is force per unit Area. How can

you derive the formula P=ρgh from P=F/A.

b. Temperature
-degree or intensity of heat present in a
substance
- common temperature scales: Celsius,
Kelvin, Fahrenheit, Rankine

ustchesaa1920@gmail.com By: Mark Fenix

 UNIVERSITY OF SANTO TOMAS
CHEMICAL ENGINEERING SOCIETY
CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS

Standard Temperature
o STP: 0 oC
o SATP: 25 oC

Properties of water
Celsius Fahrenheit
Boiling 100 212
Point
Freezing 0 32
Point
Increments 100 180

K= C + 273.15
R= F+ 460 ISOTHERM:

Example Problem 2: 5 mins

Derive the formula for the conversion of Celsius to
Fahrenheit and vice versa. Write your solution and
answer on the space provided.

Example Problem 3: 5 mins

At what temperature will the Fahrenheit scale and
Celsius scale be the same? Write your solution and
answer on the space provided.
ISOBAR
1A.2 Equations of state

Boyle’s law: pV =constant, at constant n, T

Charles’s law: V = constant × T, at constant n, p
Gay-Lussac’s Law: p = constant × T, at constant n,V
Avogadro’s principle: V = constant × n at constant p, T

Perfect Gas equation of state:

P=nRT/V
It is the approximate equation of state of any gas, and
becomes increasingly exact as the pressure of the gas
approaches zero

ustchesaa1920@gmail.com By: Mark Fenix

 UNIVERSITY OF SANTO TOMAS
CHEMICAL ENGINEERING SOCIETY
CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS

ISOCHORE Proof:
𝑃𝐴 𝑉𝑇 𝑁𝐴 𝑅𝑇
=
𝑃𝑇 𝑉𝑇 𝑁𝑇 𝑅𝑇
𝑃𝐴 𝑉𝑇 𝑁𝐴 𝑅𝑇
=
𝑃𝑇 𝑉𝑇 𝑁𝑇 𝑅𝑇
𝑃𝐴 𝑁𝐴
= = 𝑋𝐴
𝑃𝑇 𝑁𝑇

Dalton’s law
The pressure exerted by a mixture of (perfect)
gases is the sum of the pressures that each one would
exert if it occupied the container alone.
For two ideal gases A and B prove that PT= PA+PB. Show
your derivation here. (5 mins)

Surface of possible states

Example Problem 5 (10 mins)

3 non-interacting tanks have the properties
given below.

3L 3L

P*O2=3 atm P*N2=2 atm

The surface depicts the only possible states of a perfect
gas: the gas cannot exist in states that do not
correspond to points on the surface. 6L

Example Problem 4 (5 mins) P*H2 =5 atm

In an industrial process, nitrogen is heated to 500 K in a
vessel of constant volume. If it enters the vessel at 100
atm and 300 K, what pressure would it exert at the Given the initial pressures at constant
working temperature if it behaved as a perfect gas? Temperature, calculate the total pressure when the
Answer: 167 atm tank are connected.
Answer: 3.75 atm
Mixture of gases
Partial Pressure:
PA=XAPT
XA= Mole fraction of component A
PT= Total pressure
PA= Partial Pressure of component A

ustchesaa1920@gmail.com By: Mark Fenix

 UNIVERSITY OF SANTO TOMAS
CHEMICAL ENGINEERING SOCIETY
CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS

1B The Kinetic model

Kinetic theory of gases:
It is assumed that the only contribution to the
energy of the gas is from the kinetic energies of the
molecules.

Assumptions:
1. Gas consists of atoms or molecules of mass m
undergoing random, never-ending motion
2. Molecular size is negligible: the distances over
which molecules travel are much greater than
molecular size
3. Molecules are treated as hard spheres: they
make perfectly elastic collisions with one
another and the sides of the container - this
means no energy is transferred to rotational,
vibrational or electronic modes, nor to the walls
- all energy is conserved for translation

ustchesaa1920@gmail.com By: Mark Fenix

 UNIVERSITY OF SANTO TOMAS
CHEMICAL ENGINEERING SOCIETY
CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS
Maxwell–Boltzmann distribution of speeds
The Maxwell–Boltzmann distribution of speeds gives
the fraction of molecules that have speeds in a specified
range.
The important features of the Maxwell–Boltzmann
distribution are as follows:
 includes a decaying exponential Function. Its presence
implies that the fraction of molecules with very high
speeds will be very small because e−x2 becomes very
small when x is large.
 The factor M/2RT multiplying v2 in the exponent is
large when the molar mass, M, is large, so the
exponential factor goes most rapidly towards zero
when M is large. That is, heavy molecules are unlikely
to be found with very high speeds.
 The opposite is true when the temperature, T, is high:
then the factor M/2RT in the exponent issmall, so the
exponential factor falls towards zero relatively slowly
as v increases. In other words, a greater fraction of
the molecules can be expected to have high speeds at
high temperatures than at low temperatures.
 A factor v2 (the term before the e) multiplies the
exponential. This factor goes to zero as v goes to zero,
so the fraction of molecules with very low speeds will
also be very small whatever their mass.
 The remaining factors simply ensure that, when we
sum the fractions over the entire range of speeds
from zero to infinity, then we get 1.
ustchesaa1920@gmail.com
The collision frequency is the number of collisions
made by a molecule in an interval divided by the length
of the interval.
The mean free path is the average distance a molecule
travels between collisions.
1C Real gases
Real gases have very different behaviour from
ideal gases, notably in cases of high pressure or near the
condensation point - a number of additional
interactions must be considered.
1C.1 Deviation from perfect behavior
Real gases show deviations from the perfect gas
law because molecules interact with one another.
Molecular Interactions
1. Repulsive forces: assist expansion of gas
- Significant when molecules are close to one
another
- Operative at high pressures, when
intermolecular distances are near a single
molecular diameter
2. Attractive forces: assist compression of gas
- can have influence over a long distance (close
but not touching)
-operative at moderate pressures
a. The compression factor
The compression factor of a gas can be defined
as
Where: Vm is the molar volume, V/n
By: Mark Fenix
 UNIVERSITY OF SANTO TOMAS
CHEMICAL ENGINEERING SOCIETY
CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS

p higher: C and higher order terms contribute, deviation

Ideal gas: Z = 1 from linearity
Departure from Z = 1 means that a gas is not Boyle Temperature
behaving as an ideal gas Perfect gas: dZ/dp = 0 (since Z = 1), but in a real gas

Intermediate Pressure: Z < 1

Compression is favored, due to dominance of
attractive forces

High Pressure: Z > 1 At low T: initial dZ/dp < 0, B is negative

Expansion is favored, as repulsive forces come
into play
At high T: initial dZ/dp > 0, B is positive
(Correspond to the first order B coefficients at these
temperatures)
The temperature at which the initial slope is zero is the
Boyle Temperature, TB, where B = 0 (real gas
corresponds to an ideal gas)
It is at this temperature that the attractive forces and
the repulsive forces acting on the gas particles balance
out

b. Virial Coefficients
For a real gas with large molar volumes
and higher temperatures, the isotherms are
almost identical to those of an ideal gas.
However, there are some small differences.

These are the virial equations of state, where

coefficients B and C have to be evaluated at each
temperature! 1C.2 van der Waals Equation
p = 0: Close to ideal gas law, but not exact
p increases: B contributes, linear relation between Z
and P
a= attractive

ustchesaa1920@gmail.com By: Mark Fenix

 UNIVERSITY OF SANTO TOMAS
CHEMICAL ENGINEERING SOCIETY
CHEMICAL ENGINEERING ACADEMIC Reinforcement
SESSIONS

b= repulsive at the flat inflection, the 1st and 2nd derivatives are
a&b are independent of temperature zero:

Example Problem 6 (10 mins)

Suppose that 10.0 mol C2H6(g) is confined to 4.860 dm3
at 27 °C. Predict the pressure exerted by the ethane
from (i) the perfect gas and (ii) the van der Waals
equations of state. Calculate the compression factor
based on these calculations. For ethane, a = 5.507 dm6
atm mol−2, b = 0.0651 dm3 mol−1.
Answer: Solve the two equations in two unknowns:
i. 50.68 atm Vm and T, then find p with the equation of state!
ii. 35.2 atm This gives
iii. 1.44

Summary of the vdW Equation

1. Perfect gas isotherms are obtained at high At this point, the critical compression factor
temperatures and large molar volumes: Zc = pcVc/RTc = 3/8
 at high T, the first term may be much
greater than the second
 if Vm is high, then Vm - b . Vm, p =
RT/Vm
2. Liquids and gases exist when cohesive and
dispersive forces are balanced:
 first term from KE and repulsion,
second term from attraction
3. Critical constants are related to the van der
Waals coefficients:

 critical temperature, Tc
 critical pressure, Pc
 critical molar volume, Vc

ustchesaa1920@gmail.com By: Mark Fenix