CY 2301

Basic Physical Chemistry:

Equilibrium and Changes

https://sites.google.com/site/hsahoo/teaching
 Important Characteristics of Gases
1) Gases are highly compressible
An external force compresses the gas sample and decreases its
volume, removing the external force allows the gas volume to
increase.
2) Gases are thermally expandable
When a gas sample is heated, its volume increases, and when it is
cooled its volume decreases.
3) Gases have Low viscosity
Gases flow much easier than liquids or solids.
4) Most Gases have low densities
Gas densities are on the order of grams per liter whereas liquids
and solids are grams per cubic cm, 1000 times greater.
5) Gases are infinitely miscible
Gases mix in any proportion such as in air, a mixture of many gases.
Substances That Are Gases under
Normal Conditions
Substance Formula MM(g/mol)
• Helium He 4.0
• Neon Ne 20.2
• Argon Ar 39.9
• Hydrogen H2 2.0
• Nitrogen N2 28.0
• Nitrogen Monoxide NO 30.0
• Oxygen O2 32.0
• Hydrogen Chloride HCl 36.5
• Ozone O3 48.0
• Ammonia NH3 17.0
• Methane CH4 16.0
 Ideal Gases

 Behave as described by the ideal gas

equation; no real gas is actually ideal
 Within a few %, ideal gas equation describes
most real gases at room temperature and
pressures of 1 atm or less
 In real gases, particles attract each other
reducing the pressure
 Real gases behave more like ideal gases as
pressure approaches zero.
 Gas Law Variables
• In order to describe gases, mathematically, it
is essential to be familiar with the variables
that are used. There are four commonly
accepted gas law variables

• Temperature
• Pressure
• Volume
• Moles
 Gas Laws
• (1) When temperature is held constant, the density of a
gas is proportional to pressure, and volume is inversely
proportional to pressure. Accordingly, an increase in
pressure will cause an increase in density of the gas and
a decrease in its volume. – Boyle’s Law

• (2) If volume is kept constant, the pressure of a unit

mass of gas is proportional to temperature. If
temperature increase so will pressure, assuming no
change in the volume of the gas.

• (3) Holding pressure constant, causes the temperature of

a gas to be proportional to volume, and inversely
proportional to density. Thus, increasing temperature of
a unit mass of gas causes its volume to expand and its
density to decrease as long as there is no change in
pressure. - Charle’s Law
 The Nature of Gases
Three basic assumptions of the kinetic
theory as it applies to gases:
1. Gas is composed of particles- usually
molecules or atoms
–Small, hard spheres
–Insignificant volume; relatively far
apart from each other
–No attraction or repulsion between
particles
 The Nature of Gases
2. Particles in a gas move rapidly in
constant random motion
–Move in straight paths, changing
direction only when colliding with one
another or other objects
–Average speed of O2 in air at 20 oC is
an amazing 1660 km/h!
(1.6km=1mile)
 The Nature of Gases
3. Collisions are perfectly elastic-
meaning kinetic energy is transferred
without loss from one particle to
another- the total kinetic energy remains
constant
Newtonian Cradle-
Where the collisions between the balls elastic?
Yes, because kinetic energy was transferred
with each collision
• Why did the balls eventually stop
swinging? The collisions were not
perfectly elastic, some kinetic energy
was lost as heat during each collision.
• At constant temperatures and low to
moderate pressures, collisions between
gas particles are perfectly elastic
 THE KINETIC THEORY OF GASES

• Gas consists of large number of particles

(atoms or molecules)
• Particles make elastic collisions with each
other and with walls of container
• There exist no external forces (density
constant)
• Particles, on average, separated by distances
large compared to their diameters
• No forces between particles except when
they collide
What happens to a ball when it
drops?
The potential energy …..but in reality the ball
of the ball loses height and
Is converted to kinetic eventually stops bouncing
energy in the ball

Why does this

happen?
How does the bouncing ball lose
energy?
• Through friction with the air (air
resistance)
• Through sound when it hits the floor
• Through deformation of the ball
• Through heat energy in the bounce
N is the number of particles in the corresponding state and ‘g’ is the
corresponding energy of the state

Boltzmann equation describes the statistical behavior of a thermodynamic

system not in thermodynamic equilibrium.
urms is defined as the square root of the average velocity-squared of the
molecules in a gas

The most probable speed, ump, is the speed most likely to be

possessed by any molecule (of the same mass m) in the system
and corresponds to the maximum value
• Gases do not always obey the ideal gas
law.
– At modest temperatures but high pressures,
the molecules get close enough together that
intermolecular attractive forces become
significant.
• Two things can happen –
– At low temperatures the gas can turn into a liquid
– At higher temperatures the gas stays a gas but behaves
a lot like a liquid this state is called a supercritical fluid
Deviations from ideal behaviour
• A real gas is most like an ideal gas when the
real gas is at low pressure and high
temperature.
• At high pressures gas particles are close
therefore the volume of the gas particles is
considered.
• At low temperatures gas particles have low
kinetic energy therefore particles have some
attractive force
• Example
• Dry ice, liquid oxygen and nitrogen
 Empirical Equations (or
Equation of State, EOS)
• Several empirical “cubic” equations have
been invented to relate P to V and T for
non-ideal gases.
– van der Waals
– Redlich Kwong
– Peng Robinson
– Redlich Kwong Suave
 van der Waals
PV  nRT or PV  RT , V  V /n

RT a
P ~  ~2
V b V

At very small specific At small specific

volumes, the volumes, the
molecules begin to attractive term is
touch which causes significant.
the pressure to rise
sharply.

One of the earliest and simplest

 van der Waals
• The values of a and b are different for
different molecules, but they are
proportionally related.

2
27 R 2Tc 1 RTc
a ,b 
64 Pc 8 Pc

van der Waals EOS

 Deviations from Ideal Gas Behavior
PV  nRT or PV  RT , V  V /n

PV
z T=300K
RT
“compressibility factor”

Ideal gas: z = 1
z < 1: attractive intermolecular forces dominate
z > 1: repulsive intermolecular forces dominate
 Van der Waals equation

 a 
 P  2  V  b   RT
At fixed P and T, V is the solution of a
cubic equation. There may be one or three
 V  real-valued solutions.

The set of parameters Pc, Vc, Tc for which the number of solutions changes
from one to three, is called the critical point. The van der Waals equation has
an inflection point at Tc.
 Isotherms
(P vs. V at constant T)

 P 
T  Tc :   0
 V T
 P 
   0 : unstable region
 V T

 Large V: ideal gas behavior.

 Only one phase above Tc.
 Unstable region: liquid+gas coexistence.
  P  Critical
RT Point
2a of van der Waals Equation
    
 V T (V  b) 2 V 3
2a (V  b) 2
 0 for V 3
(3 or 1 real roots)
RT

 2P  2 RT 6a
 2 
 
 V T (V  b) V
3 4

3a (V  b)3
 0 for V  4

RT

Both are satisfied at the critical (inflection) point, so...

Vc  3b
8a
Tc 
27 Rb
a
Pc 
27b 2
• The temperature at which it becomes
impossible to ever form a liquid regardless
of the pressure is called the critical
temperature. (Tc)
• The pressure at which there is just last
both vapor and liquid is called the critical
pressure. (Pc)
 Use of Tc and Pc

• The critical temperature and pressure are

key parameters for calculating the
relationship between P, V, and T for non-
ideal fluids using empirical EOS’s.
 Eliminate a and b from the van der Waals equation:

b  13 Vc , a  27b 2 Pc  3PV 2
c c , 

 3  1 8
 R
P  2  R
V    TR
 VR  3  3

P V T
PR  , VR  , TR  "reduced" variables
Pc Vc Tc

All gases behave the same way under similar

conditions relative to their critical point.
(This is approximately true.)
 Virial Equations
• Recall compressibility factor Z?
– Z = pVm/RT
– Z = 1 for ideal gases
• What about real gases?
– Obviously Z ≠ 1
• So how do virial equations address this
problem?
 Virial Equations
• For sophisticated calculations fitting
equations with more adjustable
parameters are used. These are called
virial equations. Some equations (like
those for water) might have 20 or more
adjustible constants…
RT BRT CRT DRT
P  ~  ~ 2  ~ 3  ~ 4  ...
V V V V
 Virial Equations
• Form
pVm/RT = 1 + B/Vm + C/Vm2 + D/Vm3 + …
pVm/RT = 1 + B’p + C’p2 + D’p3 + …
• B,B’,C,C’,D & D’ are virial coefficients
Temperature dependent
Can be derived theoretically or experimentally
 Virial Equations
• Most flexible form of state equation
– Terms can be added when necessary
– Accuracy can be increase by adding infinite
terms
• For same gas at same temperature
– Coefficients B and B’ are proportionate but not
equal to each other
 Peng-Robinson
• The vdW equation is Ok but other
empirical EOS’s are more accurate (but
more complicated) One that has a nice
balance of accuracy vs complexity is
the Peng-Robinson EOS.

RT a
P ~  ~ ~ ~
V  b V (V  b)  b(V  b)
 Peng-Robinson
• The a and b parameters are related
empirically to the critical properties:

R 2Tc2
a  0.45724 b  0.07780
RTc
Pc Pc
 Peng-Robinson
• The  parameter is temperature
dependent and also depends on another
tabulated,chemical specific, parameter
called the “acentric factor”

  
acentric factor
2
  1  S 1  Tr S  0.37464  1.54226  0.26992 2

T
Tr 
Tc
 Summary
• EOS are more accurate representations of
fluid PVT relationships than the simple
ideal gas law.
– Cubic equations of state have a good balance between simplicity
and accuracy.
– The other main type of empirical equation is a “virial” equation
that attempts to fit the PVT behavior with a long series of
“adjustment” terms:
 Gas
Liquefaction
 Liquefaction

• The refinery process of converting natural

gas or other gaseous hydrocarbons into
longer chain hydrocarbons such as
gasoline or diesel fuel
 Methods
• Compress the gas at temperatures less than its critical temperature

• Make the gas do work against an external force, causing the gas to
lose energy and change to a liquid state

• Make gas do work against its own internal forces, causing it to lose
energy and liquefy.

• Cascade process - use one liquefied gas to liquefy another

• Joule-Thomson effect - compress and then rapidly expand the gas

Liquefaction Temperatures
 Liquid Natural Gas (LNG)

• Cooled until it Liquefies @ -160°C

• Reduces volume 600 times

• Colorless, Odorless and Non-Toxic

• Safe to transport and store

• Shipped and Stored at Atmospheric

Pressure
 Natural Gas Liquefaction
Process
-161ºC
GAS GAS
Treatment
and
Purification

Storage

•Removes condensate,
CO2, Mercury, and H2S
•Causes dehydration
Refrigerant
Loop

LNG

Compression
 Environmental Advantages

• Virtually no ash, sludge or hazardous waste is produced

• Particulate emissions are approximately 95% less than

burning coal

• Over Coal, LNG has lower:

– Sulfur dioxide emissions (by 100%),
– Nitrogen Oxide emissions (by 75%)
– Carbon Dioxide emissions (by 50%)
 LNG Chain

Transmission
Gas Well Pipeline Shipping

Market

Field Liquefaction
Processing Receiving
Terminal