Lecture 02A CM1131 Physical Chemistry 1 1

Intended learning
In this lecture we will…
outcomes addressed.

(1) – characterization of (c) Make a connection

(b) Provide an
real physical systems. between temperature
explanation for the
(a) Define a perfect gas. and the kinetic energy
(2) – explain observed perfect gas equation of
per mole of a perfect
changes. state.
gas.

Lecture 02A CM1131 Physical Chemistry 1 2

 Properties of Matter Thermodynamic State Equation of State
• Can be captured • Exists when the system is • If the system is in a
mathematically using in an equilibrium state, or thermodynamic state,
thermodynamic variables. quasi equilibrium state. then this state is governed
• These variables are only • Quasi here means that the by an equation.
defined when the system system is very nearly at • Experimentally for real
is in a thermodynamic equilibrium so can be gases
state. approximated as such. 𝑝𝑉
lim 𝑍 𝑝, 𝑉, 𝑛, 𝑇 = =1
𝑝→0 𝑛𝑅𝑇

Lecture 02A CM1131 Physical Chemistry 1 3

 𝑝𝑉
lim 𝑍 𝑝, 𝑉, 𝑛, 𝑇 = =1
𝑝→0 𝑛𝑅𝑇
Is true for all values of p, V, n and T.
𝑝, 𝑉, 𝑛, 𝑇 ∈ ℝ≥0

Can we provide an explanation for 𝑝𝑉 = 𝑛𝑅𝑇?

Lecture 02A CM1131 Physical Chemistry 1 4

Experimental Propose a simple Develop the model
Observation hypothesis. and compare with
observation.

• For real gases in • Gas made up of • Apply known

the limit of low p: moving particles natural laws to the
• pV = nRT colliding with the model to obtain an
• Why is it so? walls of the equation that can
container. be compared to
observation.

Lecture 02A CM1131 Physical Chemistry 1 5

Molecular Motion
• The gas consists of molecules of mass, m, in ceaseless random motion obeying
the laws of classical mechanics.

Molecular Size
• The volume of the molecules is negligibly small.

Molecular Interactions
• The molecules interact only through brief elastic collisions with the walls of
the container, i.e., negligible interaction with each other.
Lecture 02A CM1131 Physical Chemistry 1 6
 WALL
Y

Z X

Length a

Lecture 02A CM1131 Physical Chemistry 1 7

• Pressure on something is the force per unit area applied to the something.
• The area of one of the box walls is a2.
• What is the force on one of these walls (say a YZ wall) applied by the molecules hitting it?
• Each molecule has velocity v = vxi + vyj + vzk, or linear momentum
p = mv = mvxi + mvyj + mvzk.
• The molecule will hit one YZ wall every a/vx seconds.
• Change in momentum on collision with one of the YZ walls is Dpx = 2mvx, Dpy = 0 , Dpz = 0.
• Force is the rate of change of momentum, so we have a Dpx change every a/vx seconds.
• In the first a/vx seconds one of the YZ walls is hit, then in the next a/vx seconds the second YZ wall is hit to
bring the molecule back to where it started along the x-axis.
• Thus the rate of change of momentum is F = Dpx/(a/vx) = 2mvx2/a on each wall.
• This force is being exerted on the two YZ walls of area 2a2, so the pressure on these walls due to a single
molecule must be pYZ = F / (2a2) = mvx2/V. Note that V = a3.
Lecture 02A CM1131 Physical Chemistry 1 8
 𝑚𝑣𝑥,1 2
𝑝𝑌𝑍 1 = For molecule number 1
𝑉

Total pressure on the YZ walls due to all N molecules

𝑁 2 𝑁 2 𝑁
𝑚𝑣𝑥,𝑖 𝑚 2
𝑚𝑁 𝑣𝑥 2
1
𝑝𝑌𝑍 = = 𝑣𝑥,𝑖 = because 𝑣𝑥 = 𝑣𝑥,𝑖 2
𝑉 𝑉 𝑉 𝑁
𝑖=1 𝑖=1 𝑖=1

Gases are isotropic, the pressures must be the same on all walls, so

𝑚 𝑣𝑥 2 𝑚 𝑣𝑦 2 𝑚 𝑣𝑧 2
𝑝=𝑁 =𝑁 =𝑁 therefore 𝑣𝑥 2 = 𝑣𝑦 2 = 𝑣𝑧 2
𝑉 𝑉 𝑉

Lecture 02A CM1131 Physical Chemistry 1 9

Recall that linear or translational kinetic energy of particle i is given by

1
𝐸K (𝑖) = 𝑚𝑣𝑖 2
2

The total translational kinetic energy of all of the gas particles, i = 1, 2, 3, …, N is

𝑁 𝑁 𝑁
1 2
1 1
𝐸K = 𝐸K (𝑖) = 𝑚 𝑣𝑖 = 𝑚𝑁 𝑣 2 𝑣2 = 𝑣𝑖 2 𝑣2 ≠ 𝑣 2
2 2 𝑁
𝑖=1 𝑖=1 𝑖=1

Lecture 02A CM1131 Physical Chemistry 1 10

 𝑚 𝑣𝑥 2 1
𝑝=𝑁 𝐸K = 𝑚𝑁 𝑣 2
𝑉 2
𝑣 2 = 𝑣𝑥 2 + 𝑣𝑦 2 + 𝑣𝑧 2 and we know 𝑣𝑥 2 = 𝑣𝑦 2 = 𝑣𝑧 2

𝑣 2 = 3 𝑣𝑥 2

1 3 2 𝐸K
𝐸K = 𝑚𝑁 𝑣 = 𝑚𝑁 𝑣𝑥 2
2
so 𝑣𝑥 2 =
2 2 3 𝑚𝑁

2
2 𝐸K 2 2
𝑝𝑉 = 𝑁𝑚 𝑣𝑥 = 𝑁𝑚 = 𝐸K 𝑝𝑉 = 𝐸K
3 𝑚𝑁 3 3

Lecture 02A CM1131 Physical Chemistry 1 11

 2
𝑝𝑉 = 𝐸K 𝑝𝑉 = 𝑛𝑅𝑇
3
Model 1.0 relates the temperature of n moles of
a perfect gas to the total translational kinetic
energy of all the gas particles.
2 𝐸K 3
𝐸K = 𝑛𝑅𝑇 or = 𝑅𝑇
3 𝑛 2
By measuring the temperature of a perfect gas
you are directly measuring the total translational
kinetic energy per mole of the gas.
Translational
𝐸K
𝑇∝ K.E. per mole
𝑛
Lecture 02A CM1131 Physical Chemistry 1 12
 Model 1.0 for a perfect gas
A perfect gas obeys the requires (a) molecules
equation of state: move randomly but obey
pV = nRT the laws of classical
mechanics.
Model 1.0 for a perfect gas
requires (b) the volume
occupied by all the
molecules to be negligibly
small.

Model 1.0 for a perfect gas

requires (c) insignificant
intermolecular interactions
and elastic collisions with
the container walls.
Model 1.0 for a perfect gas
Model 1.0 for a perfect gas
provides:
relates T  EK/n
pV = ⅔ EK

Lecture 02A CM1131 Physical Chemistry 1 13

Lecture 02B CM1131 Physical Chemistry 1 1
 Intended learning
In this lecture we will…
outcomes addressed.

(1) – characterization of
real physical systems.
See the three main ways Improve the perfect gas Make note of some
(2) – explain observed
real gases differ from model to better account equations of state for
changes.
perfect gases for real gas behaviour real gases
(5) – independent
learning

Lecture 02B CM1131 Physical Chemistry 1 2

Defined a Perfect Gas Modeled a Perfect Gas We discovered from our
• A perfect gas obeyed the • Molecules moved randomly, but model that…
equation of state: obeyed the laws of classical • pV = ⅔ EK.
pV = nRT mechanics.
• T  EK/n
• The volume occupied by the
molecules was negligibly small.
• Insignificant intermolecular
interactions and elastic collisions
with the container walls.

Lecture 02B CM1131 Physical Chemistry 1 3

 • Recall Boyle’s experimental
observations.
• Experimental observations
in the pressure range used
clearly showed 𝑝 ∝ 𝑉 −1 .
• Let’s consider a specific
case, 0.1 mol of N2 at 298K.

Lecture 02B CM1131 Physical Chemistry 1 4

 N2, T = 298 K, n = 0.1 mol N2, T = 298 K, n = 0.1 mol
10 1200
9

8 1000
Experiment
7
Perfect Gas 800
6
p / atm

p / atm
5 600
4
400 Experiment
3
Perfect Gas
2
200
1

0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0 50 100 150 200 250 300 350 400 450
1/V / L-1 1/V / L-1

Up to 10 atm, N2 matches a perfect gas quite nicely At very high p substantial deviations from perfect
behavior occurs

Lecture 02B CM1131 Physical Chemistry 1 5

 N2, T = 298 K, n = 0.1 mol N2, T = 298 K, n = 0.1 mol
1200 230
pexperiment > pperfect
1000 Perfect Gas 210
Experiment
Experiment 190
Perfect Gas
800
Real gas resists compression 170
p / atm

p / atm
600 150
at extreme pressures
130
400
110
200
90 pexperiment < pperfect
0 70
0.00 0.01 0.02 0.03 0.04 0.05 0.0100 0.0125 0.0150 0.0175 0.0200 0.0225 0.0250 0.0275 0.0300
V/L V/L

Lecture 02B CM1131 Physical Chemistry 1 6

• Introduce to make deviations from Compression Factor for N2
1.14
perfect behavior more obvious. 1.12

• Could be also defined as 1.10

1.08 V > V0
𝑉𝑚 𝑉 𝑝𝑉
𝑍= 0= 0=
1.06

𝑉𝑚 𝑉 𝑛𝑅𝑇 1.04

Z
1.02

• Where the superscript “0” means 1.00

V < V0 Still only ~4%
the V a perfect gas would have. 0.98
different from 1
• Where the subscript “m” means
0.96

0.94
“molar”, Vm = V / n. 0 25 50 75 100 125 150 175 200 225 250 275 300
p / atm
• Z for a perfect gas is 1 always
Lecture 02B CM1131 Physical Chemistry 1 7
 CO2, T = 298 K, n = 0.1 mol CO2, T = 298 K, n = 0.1 mol
30 200
180
25 Deviation Perfect Gas 160 Perfect Gas

20
creeping in Experiment 140 Experiment
120

p / atm
p / atm

15 100
80
10 Pretty much a 60
perfect gas here 40
5
20

0 0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200

V/L V/L

Lecture 02B CM1131 Physical Chemistry 1 8

 CO2, T = 298 K, n = 0.1 mol • Can you find the physical
85.0 explanation for the three effects?
1. 𝑉 0 < 𝑉 at extreme pressures
80.0
Perfect Gas
Experiment
75.0

2. 𝑉 0 > 𝑉 at moderate pressure

p / atm

70.0

65.0
and 𝑉 0 ≈ 𝑉 at low pressures
60.0 3. A “flat bit” in the p-V diagram
55.0
for some gases under certain
0.005 0.010 0.015 0.020 0.025
V/L
0.030 0.035 0.040 0.045
conditions.

Lecture 02B CM1131 Physical Chemistry 1 9

The scientific method at work…

Maybe classical mechanics

Careful examination of doesn’t work?
Model must have something
experimental data reveals
wrong with it, because it doesn’t Maybe the molecules are not
significant deviation from perfect
predict these. Examine negligibly small?
gas behavior under various
assumptions. Maybe intermolecular
conditions.
interactions are not insignificant?

Perfect gas works very well at low

pressures, or large volumes, or
Try easiest modifications first.
high temperatures.
Keep modifications as simple as
Shall stick with it, but modify it to
possible.
try and account for the
deviations.

Lecture 02B CM1131 Physical Chemistry 1 10

 Molecules are not insignificantly small. But p is now always predicted to be > pperfect

The volume the molecules have to move around in is less This is not true always!
than V due to the physical size of the molecules.
220 Experiment
Perfect Gas
Let b be the volume occupied by a mole of molecules. 170

p / atm
The amount of space available for the molecules to 120
Here p < pperfect
move around in is thus 𝑉 − 𝑛𝑏 less the space occupied by the molec’s 70
0.010 0.015 0.020 0.025 0.030
Volume of the container
V/L
Substitute this into the perfect gas equation
𝑛𝑅𝑇 How does this equation work?
𝑝= Subtract some pressure from the formula!
𝑉 − 𝑛𝑏 1200
Perfect Gas
1000
800 Experiment The term should vanish 𝑛𝑅𝑇 𝑛 2
p / atm

Note that V 600 at large V. 𝑝= −𝑎

must be > nb 400 𝑉 − 𝑛𝑏 𝑉
2
Subtract 𝑎 𝑛/𝑉
200
always. 0
van der Waals equation of state
-0.01 0.01 0.03 0.05
V/L
Lecture 02B CM1131 Physical Chemistry 1 11
 When a and b are zero,
𝑛𝑅𝑇 𝑛 2
what does the van der
𝑝= −𝑎
Gas a/ b/ 𝑉 − 𝑛𝑏 𝑉 Waals equation of state
(atm L2 mol-2) (L mol-1) become?
He 0.03457 0.0237
Ne 0.2135 0.01709
Ar 1.355 0.0320
H2 0.2476 0.02661
N2 1.408 0.03913
O2 1.378 0.03183
Cl2 6.579 0.05622
NH3 4.225 0.0371
CH4 2.283 0.04278
CO2 3.640 0.04267
H2O 5.536 0.0305
Lecture 02B CM1131 Physical Chemistry 1 12
 Perfect Gas van der Waals Gas

Lecture 02B CM1131 Physical Chemistry 1 13

Most general is the Virial equation of state
𝑛𝑅𝑇 𝑛 𝑛 2 𝑛 3
Can be made as accurate as desired by
𝑝= 1+𝐵 𝑇 +𝐶 𝑇 +𝐷 𝑇 +⋯
𝑉 𝑉 𝑉 𝑉 including more terms.

van der Waals equation of state

𝑛𝑅𝑇 𝑛 2
𝑝= −𝑎 Already met this one.
𝑉 − 𝑛𝑏 𝑉

Berthelot equation of state

𝑛𝑅𝑇 𝑎 𝑛 2
𝑝= − Slight modification to van der Waals
𝑉 − 𝑛𝑏 𝑇 𝑉

Dieterici equation of state

𝑛𝑅𝑇𝑒 −𝑎𝑅𝑇𝑉/𝑛
𝑝=
𝑉 − 𝑛𝑏
Lecture 02B CM1131 Physical Chemistry 1 14

We examined the behaviour of real
gases more closely and found three
differences between them and the
perfect gas.
The third difference occurs for
some real gases at specific
temperatures. Somewhere along
the p-V curve the V can be made
smaller without any increase in p
after which additional compression
requires immense pressures.
Lecture 02B
The first difference occurs at very
high pressures (generally greater
than 10 atm) where perfect gases
continue to be compressed, but
real gases resist compression.
We examined van der Waals’ model
for a real gas which was a
modification to the perfect gas
model, and saw how this altered
the perfect gas equation of state.
CM1131 Physical Chemistry 1
The second difference occurs at
moderate pressures where real
gases are compressed slightly more
than perfect gases.
We briefly looked at alternative real
gas equations of state noting that
the most general of these was a
mathematical infinite series called
the Virial equation of state.
15