JF Chemistry CH 1101

Introduction to Physical
Chemistry
2012-2013
Properties of Gases,
Basic Thermodynamics,
Dr Mike Lyons
School of Chemistry
Trinity College
email: [email protected]

JF

Contact Details:

Dr Mike Lyons SF

School of Chemistry
Trinity College
Dublin 2.

email: [email protected]

SF-SS
16 lectures. 8 tutorials
Lecture slides/problem sheets
sent via class email before
each lecture.
Also available on Chem. School
web site and on Web CT after module finishes.

1
 Recommended reading
• Peter Atkins & Julio de Paula (AdP E5), Elements of Physical Chemistry, OUP, 5th
Edition, 2009, Chapter 0, pp.1-14 and Chapter 1, pp.15-40.
• Burrows, Holman, Parsons, Pilling, Price, Chemistry3, OUP, 2009, Chapter 7,
pp.301-315.
• Kotz, Treichel, Townsend, Chemistry and Chemical Reactivity, 7th Edition, Brooks
Cole C Engage Learning, Chapter 11, pp.514-553.
• Peter Atkins & Julio De Paula (AdP PC8), Physical Chemistry, 8th Edition, OUP
2006.

Robert Boyle 1627-1691 Jacques Charles 1746-1823 Amedeo Avogadro 1776-1856 John Dalton 1766-1844

‘Thermodynamics is the only physical theory of

universal content which, within the
framework of the applicability of its basic
concepts, I am convinced will never be
overthrown’. - Albert Einstein.

‘The law that entropy always increases- the

Second Law of Thermodynamics- holds, I
think, the supreme position among the laws of
Physics. If someone points out to you
that your pet theory of the universe is in
disagreement with maxwells equations-
then so much the worse for maxwell’s equations.
If it is found to be contradicted by
observation- well, these experimentalists do
bungle things from time to time.
But if your theory is found to be against the
Second law of Thermodynamics I can give
you no hope: there is nothing for it but to
collapse in deepest humiliation.’
-Sir Arthur Eddington.

‘Thermodynamics is a funny subject. The first

time you go through it, you don’t
understand it at all. The second time you go
through it, you think you understand it
, except for one or two small points. The third
time you go through it, you know
you don’t understand it, but by that time you are
so used to it it doesn’t bother you anymore.’
- Arnold Sommerfeld.

2
 Lecture 1

Gas Laws and the ideal gas

equation.

The three states of matter.

3
 General properties of gases
• A gas is a state of matter which fills any
container it occupies.
• Molecular picture of gas:
– Collection of widely separated molecules in
random chaotic motion. Hence molecules move
through space freely to fill any volume.
• Gases are highly compressible hence readily
confined to smaller volume.
• Gases respond readily to changes in
temperature and occupy a larger volume when
heated and a smaller volume when cooled.
• Fundamental properties of gases described in
terms of pressure P (units: Nm-2, atm etc),
Volume V (units: L (or dm3), m3 etc),
temperature T (unit: K) and amount (unit: mol).
• General properties of gases are described in
terms of three empirical laws developed by
Boyle, Charles and Avogadro which may be used
to predict the behaviour of a gas under given
conditions of temperature, pressure and volume.

4
 ∆F dF
P = Lim =
∆A→0 ∆A dA

Pressure P defined as
Force per unit area.

5
 Table 5.2 Common Units of Pressure

Unit Atmospheric Pressure Scientific Field

pascal(Pa); 1.01325x105Pa; SI unit; physics, chemistry

kilopascal(kPa) 101.325 kPa
atmosphere(atm) 1 atm* chemistry

millimeters of 760 mm Hg* chemistry, medicine, biology

mercury(Hg)

torr 760 torr* chemistry

pounds per square 14.7lb/in2 engineering

inch (psi or lb/in2)

bar 1.01325 bar meteorology, chemistry,

physics

*This is an exact quantity; in calculations, we use as many significant figures as necessary.

Some basic Physics

liquid dF

ρ
h
dA
Volume V of liquid cylinder = h dA
Mass m of cylinder = ρh dA
Weight of cylinder = mg = ρhg dA
Force acting downwards dF = ρhg dA
vacuum
Pressure P = dF/dA = ρgh
Y

PX – PY = ρgh h patm
PY = 0 (Vacuum)
PX = Patm (Patm acts on same
Plane as point X) X

Patm = ρgh
See AdP 5th ed.
ρHg = 13.6 x 103 kg m-3 Fig. 0.3 and Derivation 0.1
h = 760 mm p.6.

6
7
Chemistry3 pp.303-304.
Kotz, Ch.11, pp.517-519.

8
The volume of a gas decreases as the A good test of Boyle’s Law is to plot the
Pressure on it is increased. pressure P against 1/V at constant
For a sample which obeys Boyle’s Law temperature where a straight line
and that is kept at constant temperature should be obtained.
the P-V relationship is hyperbolic.

Chemistry3 pp.304-305.
Kotz, Ch.11, pp.519-521.

9
 From this observation we define the Thermodynamic
Note that the V versus T curves all Temperature (Absolute) Scale as follows:
Intersect at a single point termed T (K) = θ (ºC) +273.15
The absolute zero of temperature. where T denotes the thermodynamic temperature
This is the lowest attainable temperature in degrees Kelvin (K) and θ represents the temperature
And has the value – 273.15 ºC. in degrees Celsius (ºC).

10
 Chemistry3 p.305
Avogadro’s Principle.

• Under conditions of constant temperature and

pressure, equal volumes of gases contain the
same number of molecules.
• In simple terms doubling the amount (unit: mol)
of molecules in a gas sample results in a doubling
of the volume of the gas, if the pressure and
temperature are held constant.

V ∝n Amount of gas (mol)

V
= K = constant
n
The quantity V/n is termed the molar volume VM.
Hence Avogadro’s Law states that a gas containing
1 mole of X molecules occupies the same volume (molar Molar volume of a perfect gas at
Volume) as one consisting of 1 mole of Y molecules, Standard Ambient Temperature and
Whatever the identity of the substances X and Y. Pressure (SATP: 298.15 K and P = 1 bar)
Hence Avogadro’s principle implies that the molar volume Is VM = 24.7896 dm3mol-1 and at
of a gas should be the same for all gases at the same Standard Temperature and Pressure
Pressure and temperature. (STP: T = 0ºC, P = 1 atm)
VM = 24.414 dm3mol-1 .
Reference: AdP5: p.19.

11
 Chemistry3 p.306, p.309-310.
Ideal Gas equation of State. Kotz, Ch.11, pp.521-524.

Constant T,n

1
V∝
P
V ∝T Constant P,n

V ∝n
Constant T,P

nT
V∝ PV PVM
P Ideal Gas
Equation of State
R= =
 nT  nT T
V = R 
P
PV = nRT The numerical value of R will depend
On the units adopted for P, V and T.
R = Universal Gas Constant

Determination of Universal Gas Constant R.

PV PVM
R= =
nT T
Assume 1 mol gas ( n = 1). At STP, P = 1 atm, T = 273.15 K, VM = 22.414 dm3.

R=
(1 atm)× (22.414 dm3 ) = 0.0821 dm3atmK −1mol −1
(1 mol )× (273.15 K )

In SI units: n = 1, P = 1 atm = 1.013 x 105 N m-2, VM= 22.414 x 10-3 m3

since 1 dm3 = 1 L = 10-3 m3. 1 Nm = 1 J

R=
(1.013×10 Nm )× (22.414 ×10
5 −2 −3
m3 ) = 8.314 Nm mol −1
K −1 = 8.314 J mol −1K −1
(1 mol )× (273.15 K )
PiVi Pf V f Can re-arrange
= nR = nR equation to
Ti Tf
Initial State Final State express any one
Pi,Vi,Ti,n Pf,Vf,Tf,n PiVi Pf V f of the six quantities
=
Ti Tf in terms of the other
five.

12
 Ideal Gas Equation of State
(IGEOS)

PV = nRT

The expression PV = nRT is termed the ideal gas

equation of state (IGEOS). This defines an ideal
gas.
An equation of state is a mathematical
Expression relating the pressure P, volume V and
Temperature T and amount of substance n
present in a sample.
Equations of state are very useful because they
Make it possible to calculate one particular
property (either P,V,T or n) once we have values
assigned to the other three.
Most gases obey the IGEOS approximately under
normal lab conditions.
All gases obey IGEOS more and more closely as
the gas pressure is reduced and the gas becomes
more dilute.

Equation of state of gases

• The state of a gas sample
can be specified by giving
the values of the pressure P,
volume V, temperature T and
amount n.
• P,V,T and n are not
Ideal Gas
independent of one another.
equation
• Any gaseous substance will of state
be described by an equation
of state which describes the
relationship between PV = nRT
pressure P and the other Van der Waals equation
variables V,T and n. of state
• Mathematically the equation
of state is expressed as: n2 a
(P + )(V − nb) = nRT
P = F (n,V , T ) V2
Takes molecular interactions into account

13
 Density of an ideal gas.

We can easily calculate the density ρ of an ideal gas.

Mass of gas m =amount (mol) of molecules in sample X mass per mole (g/mol) m=nM
Gas density ρ = mass of sample / volume of sample. m nM
ρ= =
PV = nRT V V
From Ideal Gas equation n P
=
V RT

Hence gas density ρ is n PM

ρ= M=
V RT

For a given type of gas (fixed M) the density ρ is directly

proportional to the pressure P at constant temperature T.
Furthermore if the pressure P is constant the density is inversely
proportional to the temperature T. Hence as the temperature
is increased, the density of the gas decreases (secret
behind operation of hot air balloon).
For a fixed temperature T and pressure P the density of a gas is
Directly proportional to the molar mass M of the gas.
Hence gas molecules of high molar mass are more dense than
gas molecules of low molar mass.
Note that many sensible predictions can be extracted from Kotz, Ch.11, pp.525-526.
mathematical formulae. See also Kotz section 11.4
on gas laws & chemical
Reactions, pp.527-530.

Kotz, Section 11.5, pp.530-532.

14
 Mixtures of Ideal Gases : Daltons Law of Partial Pressures.
We can extend our discussion to mixtures of ideal gases. We
can expect that a mixture of gases that do not react with
each other will behave like a single pure gas.
Hence we introduce the partial pressure p of a gas in a gas
mixture as follows:
this is the pressure which the gas component would exert
if it alone occupied the container.

Daltons Law: For a system containing two or more different

gases, the total pressure P is the sum of the individual
partial pressures p that each gas would exert if it
alone occupied the container.

The total pressure P of a gas mixture containing k

k
component gases each of partial pressure pk is:
P = p1 + p2 + p3 + ..... + pk = ∑ pi
We consider a system of two ideal gases A,B contained i =1

in a volume V at a temperature T.
gas partial pressures are pA, pB and amounts are nA, nB.

n A RT
p AV = n A RT ⇒ pA = p A n A RT  V  nA n
=  = = A
V  (n A + nB )RT  n A + nB
V
P n
n RT
pBV = nB RT ⇒ p B = B
V pB nB RT  V  nB nB
=  = =
P V  (n A + nB )RT  n A + nB n
= (n A + nB )
n RT nB RT RT
P = p A + pB = A +
V V V

nA n
XA = = A
We define the mole fraction X of gases A and B as n A + nB n n = n A + nB
nB n
XB = = B
Hence we arrive at expressions for the partial n A + nB n
Pressures of each component gas in terms of the
Mole fraction and the total pressure.
pA = X A P
We note that the sum of the
mole fractions in a mixture must pB = X B P
equal unity.
p A pB p A + pB P
XA + XB = + = = =1
P P P P
X A + XB =1
If only A is present then XA=1 and
XB = 0. When only B is present XA = 0 and
XB = 1. When both are present in equal
Amounts then XA = XB = 0.5.
pi = X i P
k
General case for a k component mixture. P = ∑ pi
i =1
k

∑X
i =1
i =1

15