1

Engineering
Thermodynamics
WEEK 7-8
Enthalpy 2

A thermodynamic quantity equivalent to the total heat content of a

system. It is equal to the internal energy of the system plus the product of
pressure and volume.
 Heat is absorbed when breaking bonds
Solid → liquid → gas
 Heat is released when making bonds
Gas → liquid → solid
 This expression is consistent with our definition of enthalpy, where we
stated that enthalpy is the heat absorbed or produced during any process
that occurs at constant pressure. At constant pressure, the change in
the enthalpy of a system is equal to the heat flow: ΔH=Qp
Enthalpy => Heat of Reaction 3
4
5
6
 Important Characteristics of Gases 7

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
8
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
 9
Kinetic Molecular Theory
 To fully understand the world around us requires that we have a good
understanding of the behavior of gases. The description of gases and their
behavior can be approached from several perspectives.
 The Gas Laws are a mathematical interpretation of the behavior of gases.
 However, before understanding the mathematics of gases, a chemist must
have an understanding of the conceptual description of gases. That is the
purpose of the Kinetic Molecular Theory.
 10
 Kinetic Molecular Theory
 The Kinetic Molecular Theory is a single set of descriptive characteristics of a substance
known as the Ideal Gas.
 All real gases require their own unique sets of descriptive characteristics. Considering the
large number of known gases in the World, the task of trying to describe each one of them
individually would be an awesome task.
 In order to simplify this task, the scientific community has decided to create an imaginary
gas that approximates the behavior of all real gases. In other words, the Ideal Gas is a
substance that does not exist.
 The Kinetic Molecular Theory describes that gas. While the use of the Ideal Gas in
describing all real gases means that the descriptions of all real gases will be wrong, the
reality is that the descriptions of real gases will be close enough to correct that any errors
can be overlooked.
 The Nature of Gases 11

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 12

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)
 13
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
 14
Ideal Gas Model 
Kinetic Molecular Theory (KMT) for an ideal gas states that all
gas particles:
 are in random, constant, straight-line motion.
 are separated by great distances relative to their size; the volume
of the gas particles is considered negligible.
 have no attractive forces between them.
 have collisions that may result in the transfer of energy between
gas particles, but the total energy of the system remains constant.
 Ideal vs. Non-Ideal Gases 15

x x

 Kinetic Theory Assumptions

 Point Mass
 No Forces Between Molecules
 Molecules Exert Pressure Via Elastic Collisions With Walls
 Ideal vs. Non-Ideal Gases 16

 Non-Ideal Gas
 Violates Assumptions
Volume of molecules
Attractive forces of molecules
 Deviations from ideal behaviour 17

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
 Boyle’s Law 18

 Hyperbolic Relation Between Pressure and Volume

p – V Diagram

T1 T T T3 >T2>T1
2 3

isotherms
p

V
 Charles’ Law 19

 Linear Relation Between Temperature and Volume

Isobars

T – V Diagram
 Gay-Lussac’s law: 20

Temperature & pressure

 As P then T
 At constant V, n

Remember all Temperatures must be in KELVIN

 Avogadro’s Principle 21

 Equal
volumes of gases contain equal
numbers of moles
at constant temp & pressure
true for any gas

n
 Ideal Gas Law 22

The equality for the four variables involved

in Boyle’s Law, Charles’ Law, can be written

PV = nRT

R = ideal gas constant

 PV= nRT 23

R is known as the universal gas constant

Using STP conditions

R = PV = (1.00 atm)(22.4 L)
nT (1mol) (273K)

= 0.0821 L-atm
mol-K
 Learning Check 24

Dinitrogen monoxide (N2O), laughing gas, is used

by dentists as an anesthetic. If 2.86 mol of gas
occupies a 20.0 L tank at 23°C, what is the pressure
(mmHg) in the tank in the dentist office?
 25
Solution
Set up data for 3 of the 4 gas variables
Adjust to match the units of R

V = 20.0 L 20.0 L

T = 23°C + 273 296 K

n = 2.86 mol 2.86 mol

P = ? ?
Rearrange ideal gas law for unknown P
26
P = nRT
V

Substitute values of n, R, T and V and solve for P

P = (2.86 mol)(62.4L-mmHg)(296 K)
(20.0 L) (K-mol)

= 2.64 x 103 mm Hg
 Absolute Zero 27

 The greater the atomic and molecular motion, the greater

the temperature is of a substance.

 Ifall atomic and molecular motion would stop, the

temperature would be at absolute zero (0 Kelvin or -273
o
C)
 Diffusion and Effusion 28

 Diffusion – describes the movement of one material through another.

Particles diffuse from an area of high concentration to low concentration
 Effusion – gas escapes through a tiny opening. The heavier the molecule, the
slower it will effuse or diffuse
Diffusion and Effusion 29

Diffusion verses Effusion:

The diffusion is the movement of one
gas into another while effusion is the
movement of gas through the aperture.
 30
Kinetic Theory of Gasses
i. why the pressure of a gas increases when it is
compressed at constant temperature?
ii. why the pressure of a fixed volume of gas
increases with temperature?

iii. why the volume of a gas increases when

heated at constant pressure?
 i. why the pressure of a gas increases when it is compressed
at constant temperature? 31

Kinetic theory and Boyle’s Law

 When a gas is
compressed at constant
temperature,
 the molecules have less
volume to move and hit
the wall of the container
more frequently.
 As a result, pressure will
increases.
 ii. why the pressure of a fixed volume of gas increases with
temperature? 32
Kinetic theory and Pressure Law

 Astemperature rises, the

molecules move faster,
 The molecules will hit the walls
of the container frequently and
violently.
 Hence, the pressure increases
 iii. why the volume of a gas increases when heated at
constant pressure? 33

Kinetic theory and Charles’ Law

 When a gas is heated, the gas
molecules move faster and
 hitthe wall of the container
violently.
 The volume of gas must
increase to keep the pressure
constant.
 So that the gas molecules hit
the wall less frequently.
Zeroth Law 34

 If A is in thermal equilibrium with B, and B is in thermal

equilibrium with C, then C will be in thermal equilibrium with A.
 When two systems are put in contact with each other, there will be
a net exchange of energy between them unless or until they are in
thermal equilibrium. That is the state of having equal temperature.
Although this concept of thermodynamics is fundamental, the need
to state it explicitly was not widely perceived until the first third of
the 20th century, long after the first three principles were already
widely in use.
 Hence it was numbered zero.
 Zeroth Law 35

 The Zeroth Law asserts that thermal equilibrium, viewed as a binary

relation, is a transitive relation (and since any system is always in
equilibrium with itself and if a system is in equilibrium with
another, the latter is in equilibrium with the former, it is furthermore
an equivalence relation).