CHEM 2011

CH 1: Introduction
CHEM 2011
CH 1: Introduction

1.1-1.5
1.1 What is Thermodynamics and Why Is It Useful?
1.2 The Macroscopic Variables Volume, Pressure and
Temperature
1.3 Basic Definitions Needed to Describe
Thermodynamic Systems
1.4 Equations of State and the Ideal Gas Law
1.5 A Brief Introduction to Real Gases

* Some concepts are covered in more detail than in the book in

order to include review material from first year.
CHEM 2011
CH 1: Introduction

CHAPTER 1
End of Chapter questions for practice:
Q: 1, 2, 3, 9, 10, 11, 15, 16, 17
P: 3, 4*, 6, 10, 13, 15, 18, 21, 22a, 23**, 27*, 32, 35, 38***
*These questions will also be taken up in tutorial.
** Note that the solutions manual has a typo (where n
H2 is calculated, that is
actually nNH3, and then XNH3=0.66)
*** 𝑤𝑟𝑜𝑛𝑔 𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝑎𝑛𝑢𝑎𝑙 𝑃 8.3145×10−2𝐿 𝑏𝑎𝑟 𝑚𝑜𝑙−1 𝐾 −1×375 𝐾
𝑖𝑑𝑒𝑎𝑙 = = 20.25 𝑏𝑎𝑟
1.54 𝐿
CHEM 2011
CH 1: Introduction

As I am squeezing through the narrow opening in the glacier and

while in contact with the ice – which direction is the heat flow in?

What is happening to the ice - why?

What is happening to my body?

How is my body temperature regulated?

sometimes the answers are intuitive, but we will learn the

Franz Josef Glacier, New Zealand reasoning behind them…
CHEM 2011
CH 1: Introduction

…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
CHEM 2011
CH 1: Introduction
BOUNDARY EXAMPLES
OF SYSTEMS

SYSTEM

A THERMODYNAMIC SYSTEM
Energy can be exchanged between the two as heat and/or work
consists of all the materials
involved in the process under
study.
The rest of the universe is
referred as the
SURROUNDINGS.
The surroundings gain the
exact amount of energy
lost by the system.
CHEM 2011
CH 1: Introduction

ISOLATED
Classification of systems
CLOSED
OPEN: matter and energy exchange
CLOSED: only energy exchange OPEN
ISOLATED: no matter nor energy exchange

HOMOGENEOUS – properties are uniform throughout

HETEROGENEOUS – contains multiple phases
CHEM 2011
CH 1: Introduction

Cells are:
A) Open systems
B) Closed systems
C) Isolated systems
CHEM 2011
CH 1: Introduction

a function or property whose

value depends only on the
present state, or condition, of
the system, not on the path
used to arrive at that state.

Examples of state functions: P, V, T

CHEM 2011
CH 1: Introduction

focus on large-scale properties of matter focus on the concept of molecules

Position, velocity, mass, describing the

microscopic motion of gas molecules

Our aim is to look at the relationship between the macroscopic properties of a gas and end up with the GAS LAWS
CHEM 2011
CH 1: Introduction

gases are easy to expand gas molecules attract each other weakly
gases are easy to compress gas molecules are far apart
gases have much lower densities than gas molecules are far apart compared
liquids and solids to those in liquids and solids

gases expand to fill a container (diffusion) gas molecules are constantly in motion

hot gas leaks through small holes faster gas molecules move faster (greater
than cold gas (effusion) kinetic energy) at higher temperatures
CHEM 2011
CH 1: Introduction
volume of molecules is negligible
mostly empty space
compared to their average separation
pressure is the manifestation of the
gases molecules are in constant motion
molecules hitting the wall of a container
gases are disordered unlike solids
assume negligible interactions between
an ideal gas
gas molecules
average motion of gas molecules
increases with temperature

distribution of speeds of gas molecules

Maxwell – Boltzmann distribution
becomes broader at higher temperature
CHEM 2011
CH 1: Introduction KINETIC ENERGY

How can a material store energy? In gases molecules are in In solids molecules
rapid random motion vibrate like springs
On the molecular scale, we think in terms of:
MOLECULAR VIBRATION MOLECULAR ROTATION
THERMAL ENERGY = kinetic energy of
molecular motion (translational, rotational,
and vibrational)
measured by finding the temperature. POLARIZABLE MOLECULES IN AN ELECTRIC FIELD

CHEMICAL BOND ENERGY = potential

energy stored in molecular bonds
CHEM 2011
CH 1: Introduction

definition
Properties Describe or identify matter.

Properties of matter can be

divided into physical properties
intensive properties do not depend on amount
and chemical properties.
Density, colour, boiling point
Properties
of matter

extensive properties do depend on amount

Mass, volume
CHEM 2011
CH 1: Introduction P
Example: Using ideal gas law T=
R

ρ1 = ρ2
P1 ≠ P2
TEMPERATURE is an T1 ≠ T 2
abstract quantity. Two systems with rigid walls
and the same molar density
How do we define it? have different temperatures.

Hot or Cold
Temperature is measured indirectly e.g.
• measuring the volume of mercury confined to a narrow capillary
• measuring electrical resistance of a platinum wire
CHEM 2011
CH 1: Introduction EQUILIBRIUM refers to exchange of matter or energy across a boundary
Equilibrium for a variable established when variable does not change in time

(Varsystem = Varsurroundings)
Walls move

BOUNDARY CHARACTERISTICS REQUIRED FOR EQUILIBRIUM:

molecules
▪ Are walls permeable in both directions
Q to all species? (concentration)
▪ Are walls moveable? (pressure)
CHEM 2011 The two systems are brought together so that the walls are in intimate contact. Even after
CH 1: Introduction a long time has passed, the pressure in each system is unchanged.

The walls are adiabatic. An adiabatic system does not permit

the passage of energy as heat through its boundary even if
there is a temperature difference between the system and its
surroundings.

ISOLATED SYSTEM
between systems exists if
P1=P2 for gaseous
The two systems are brought together so that the walls are in intimate contact, but in this
systems with the same case after a long time has passed, the pressures are equal.
molar density.

The walls are diathermal. A diathermal system permits the

passage of energy as heat through its boundary.

OPEN/CLOSED SYSTEM
CHEM 2011
CH 1: Introduction
Real walls are never totally adiabatic. Order the following walls
in increasing order with respect to being diathermal:

1-cm-thick concrete
1-cm-thick vacuum
1-cm-thick copper
1-cm-thick cork

A) concrete < vacuum < copper < cork

B) vacuum < copper < cork< concrete
C) copper < concrete < cork < vacuum
D) vacuum < cork < concrete < copper
E) copper < copper < concrete < cork
CHEM 2011
CH 1: Introduction

Two systems that are separately in

thermal equilibrium with a third
system are also in thermal OBJECT 1 OBJECT 2
equilibrium with one another.
CHEM 2011 Amount (n) g, l, s
CH 1: Introduction
Temperature (T) g, l, s

Volume (V) g, l

Pressure (P) g

F m a
Pressure (P) = =
A A
Pressure (P) = force exerted over an area

N kg
SI units : = 2
= 2 = 1Pa Pascal
m ms
Other units : 1atm = 101.3 kPa = 1.01325 bar = 760 mmHg = 760 Torr

Don’t forget basic metric prefixes! …(μ) micro, m(mili), k (kilo), M (mega), G(giga)…
CHEM 2011
CH 1: Introduction

• Weight of Hg causes level in tube to drop until

PHg = Patm

The average pressure at sea level will support a

column of 760 mm of mercury.
Pressure unit of “atmospheres” P = atmospheric pressure
1 atm = 760 mm Hg = 760 Torr (after Torricelli) Patm = ghd h = height of liquid column
d = density of the liquid
CHEM 2011
CH 1: Introduction

focus on the concept of molecules

• In this section we want to look at the

KMT that explains the gas laws
• KMT has 5 postulates

Position, velocity, mass, describing the

microscopic motion of gas molecules
CHEM 2011
CH 1: Introduction POSTULATES
1. Gas consists of tiny particles (atoms or molecules)
moving completely randomly
2. Volume of particles is negligible compared to total
volume occupied by gas (i.e. large separation
between individual gas molecules)
3. No attractive or repulsive forces between particles.
4. Gas molecules collide with one another (and other
things) without energy loss (elastic collisions)

5. The average kinetic energy of gas molecules is

proportional to temperature (Note: KE = ½mv2)
CHEM 2011
CH 1: Introduction 𝐾𝐸𝑎𝑣𝑔 = ½𝑁𝐴 𝑚𝑢2 (NA is Avogadro’s number)

but 𝑲𝑬𝒂𝒗𝒈 ∝ 𝑻

3
specifically, 𝐾𝐸𝑎𝑣𝑔 = 𝑅𝑇
2

1 3
𝑁𝐴 𝑚𝑢2 = 𝑅𝑇
2 2
The average kinetic energy of a molecule is:
3𝑅𝑇 3𝑅𝑇
½𝑚𝑢2 𝑢2 = =
𝑁𝐴 𝑚 𝑀 where M is the molar mass.
where 𝑢2 is the average of the squares
of the particle velocities. root mean square velocity (urms)

The kinetic energy of a mole of molecules is: in which urms will be in m/s if:
𝟑𝑹𝑻 R:
𝐾𝐸𝑎𝑣𝑔 = ½𝑁𝐴 𝑚𝑢2 (NA is Avogadro’s number) urms = 𝒖𝟐 = T:
𝑴
M:
CHEM 2011
CH 1: Introduction
um is the “most probable speed” (mode)
uav is the average speed (mean)
urms is the root mean square speed

All speeds are possible but not equally

likely – there will be a distribution of
speeds.
CHEM 2011
CH 1: Introduction

Lighter molar mass gases have

the distribution shifted towards
higher speeds and it broadens.
CHEM 2011
CH 1: Introduction

As the temperature increases,

the average velocity increases
and the distribution broadens.
CHEM 2011
CH 1: Introduction

The molecular vector velocity v is resolved into three

Cartesian components, vx, vy, vz

𝑣 2 = 𝒗 ∙ 𝒗 = 𝑣𝑥2 +𝑣𝑦2 +𝑣𝑧2

The particle kinetic energy, which corresponds to its

translational energy is then given by:
𝟏 𝟐 1 2 1 2 1 2
𝜀𝑡𝑟 = 𝟐
𝒎𝒗 = 2
𝑚𝑣 +
𝑥 2 𝑚𝑣 +
𝑦 2 𝑚𝑣𝑧 = 𝜀𝑡𝑟𝑥 +𝜀𝑡𝑟𝑦 +𝜀𝑡𝑟𝑧
CHEM 2011
CH 1: Introduction

The pressure on a wall of the container shown here

by the particles inside it is given by

P = F/A

Also,
F = ma
where 𝒎 is the mass of the particle and 𝒂 is its
acceleration as it changes direction of travel due to
the collision.

Pressure depends on
• How many molecules hit the wall
• How hard the molecules hit the wall
CHEM 2011
CH 1: Introduction

ASSUMPTION: The collisions are elastic!

The acceleration for each collision is the change in velocity (𝑑𝑣)

by time (𝑑𝑡), so the force of each collision in the i direction (x, y
or z) is:
𝑑𝑣𝑖 2𝑚𝑣𝑖
𝐹 = 𝑚𝑎𝑖 = 𝑚 𝑑𝑡
= ∆𝑡

If a particle collides elastically with the wall, for a straight-line

collision ∆𝑣 = 2𝑣 (i.e. ∆𝑣 = 𝑣 − −𝑣 = 2𝑣)
CHEM 2011
CH 1: Introduction

• Only particles within a distance of 𝑣∆𝑡 can reach the

wall within the time ∆𝑡.

• Particles that can collide with the wall of surface

area A will occupy the volume 𝒗∆𝒕 × A

• If we consider the x-direction, where ∆𝒙 is the

length of the box
∆𝒙 =𝒗𝒙 ∆𝒕
𝑽 = 𝑨∆𝒙

BUT, the pressure results from the collisions of a collection

of particles, not just a single particle!
V = 𝒗∆𝒕 × A Need to use an average to describe the collection of particles!
CHEM 2011
The total number of collisions is proportional to this
CH 1: Introduction
volume multiplied by the density of particles in the
container (i.e. n/V):

number of collisions = number of particles within 𝒗∆𝒕 that

are travelling in the +x direction.

1 𝑛𝑁𝐴 1
෩ A𝑣𝑥 ∆𝑡 ×
𝑁𝑐𝑜𝑙𝑙 = 𝑁× = × A𝑣𝑥 ∆𝑡 ×
2 𝑉 2

Only half are travelling towards the wall

TOTAL FORCE
2𝑚𝑣𝑥 2𝑚𝑣𝑥 𝑛𝑁𝐴 1
𝐹 = ∆𝑡 × 𝑁𝑐𝑜𝑙𝑙 = ∆𝑡 𝑉
× A𝑣𝑥 ∆𝑡 × 2

𝑛𝑁𝐴
𝐹 = 𝑉 𝐴𝑚 𝑣𝑥2
Denotes that it is an average value
CHEM 2011
The pressure on the wall is equal to the total force divided by
CH 1: Introduction
the surface area of the wall:

𝐹𝑡𝑜𝑡𝑎𝑙 𝑛𝑁𝐴
𝑃= 𝑃= 𝑚 𝑣𝑥2
𝐴 𝑉

The assumption we considered with KMT was that the average

kinetic energy (½mv2) is proportional to the temperature in Kelvin
(T) and actually equals to:

𝑚 𝑣𝑥2 𝑘𝐵 𝑇 kB = Boltzmann constant

=
2 2
Combining the expressions:
𝑛𝑁𝐴 𝑛𝑁𝐴 𝑛𝑅𝑇
𝑃= 𝑉
𝑚 𝑣𝑥2 = 𝑉
𝑘𝐵 𝑇 = 𝑉

PV = nRT R = ideal gas constant

CHEM 2011
CH 1: Introduction

focus on large-scale properties of matter

The aim is to determine the

relationship between the gas
observables (pressure, volume,
mass, temperature). The relationships are determined EXPERIMENTALLY

Isolated conditions are achieved by keeping two

of the parameters constant, while examining the
relationship between the other two.
CHEM 2011 OBSERVATIONS CONDITIONS
CH 1: Introduction Temperature = constant
mass (amount) = constant

Robert Boyle 1661

Boyle found that pressure and volume were

inversely proportional. (double the pressure
and the volume goes to one half).

As the volume of a gas decreases,

 space between gas particles and walls decreases 1 1
 gas molecules collide with surrounding surfaces more
𝑃 ∝ P= k PV= const.
𝑉 𝑉
frequently
 pressure increases. 𝑃1 𝑉1 = 𝑘 = 𝑃2 𝑉2
CHEM 2011
CH 1: Introduction

Jacque Charles 1787

CONDITIONS
Pressure = constant
mass (amount) = constant

STUDIED VT
Relationship between V and T
The volume is directly proportional to the temperature of a gas
if the quantity and pressure of the gas are kept constant (V  T). Wikimedia Commons
CHEM 2011 OBSERVATIONS CONDITIONS
CH 1: Introduction Pressure = constant
mass (amount) = constant

VT
’

▪ extend line to zero V…..intercept = -273.15 °C

ABSOLUTE ZERO = -273.15 °C
KELVIN TEMPERATURE SCALE
T (K) = T(°C) + 273.15
How do we express Charles’s Law mathematically?
Absolute temperatures are always used in gas
law and thermodynamic calculations! 𝑉 𝑉1 𝑉2
𝑉∝𝑇 V= k𝑇 𝑇
=k = =k
𝑇1 𝑇2
CHEM 2011
CH 1: Introduction

’
© 2003 by Prentice-Hall, Inc.

As T increases, kinetic energy of the particles increases

VT
 more collisions and higher energy collisions
 P will be higher
 greater V needed to keep P constant.

Q What happens if the gas is in a container that can’t expand or contract?

Pressure changes instead.
CHEM 2011
CH 1: Introduction

At atmospheric pressure of 1 bar,

dry ice, CO2, sublimates at −78.5 °C.
Assume you are in a coastal town 𝑚 𝐶𝑂2 =
and you have an empty container
with a movable piston and you put a
3.25 cm3 chunk of dry ice into that
container and you leave it at room 𝑛 𝐶𝑂2 =
temperature for a few hours
ensuring that all of it has
sublimated. What is the final
volume of the container? The 𝑉 𝐶𝑂2 =
density of dry ice is 1.6 g/cm3.
CHEM 2011
CH 1: Introduction

Which of the lines on the figure below is the best representation of

the relationship between the volume of a gas and its Celsius
temperature, other factors remaining constant?

a
b

Line: e
c
d
A) a
B) b
C) c
D) d 0
E) e 0 Temperature (C)
CHEM 2011 AVOGADRO’S HYPOTHESIS
CH 1: Introduction Equal volumes of gases at the same T and P contain
equal number of gas molecules.

CONDITIONS
Pressure = constant
Temperature = constant

STUDIED
Relationship between V and n
MOLECULAR INTERPRETATION
At fixed temperature and pressure, volume of a gas
is directly proportional to the quantity of the gas.  More particles
 more collisions
𝑽𝟏 𝑽𝟐  greater P
Vn = =k
𝒏𝟏 𝒏𝟐 P = const., T = const.  greater V needed to keep P constant
CHEM 2011
CH 1: Introduction BOYLE’S LAW CHARLES’S LAW AVOGADRO’S LAW

V  1/P VT Vn

𝒏𝑻
𝑽 ∝ 𝑷𝑽 = 𝒏𝒌𝑻
𝑷

Let’s combine Boyle’s Law, The constants have been combined to form the gas constant R.
Charles’s Law, and Avogadro’s Law
to develop a general expression IDEAL GAS LAW
that relates P, T, n and V!
PV = nRT

Depending on the conditions and R [P] [V] [n] [T]

equations used, the units of the R 8.314 J mol-1K-1 Pa m3 mol K
constant can vary. 0.08206 L atm mol-1K-1 atm L mol K
0.0831 L bar mol-1 K-1 bar L mol K
CHEM 2011
CH 1: Introduction
PV = nRT
The ideal gas law can be written in terms of moles
n = number of moles R = gas constant = 8.314 J mol-1 K-1

The ideal gas law can PV = NkT

be written in terms of
moles or molecules The ideal gas law can be written in terms of number of molecules
N = number of molecules kB = Boltzmann’s constant

how do we find it?

𝑁 𝑅
n= 𝑘𝐵 =
𝑁𝐴 𝑁𝐴
CHEM 2011
CH 1: Introduction

STP - Standard Temperature and Pressure 0 oC (273.15 K) and 105 pascals (1 bar).
Note! The earlier IUAPC definition of STP to 273.15 K and 1 atm is discontinued.

SATP - Standard Ambient Temperature and Pressure 25oC (298.15 K) and pressure of 1 bar
CHEM 2011
CH 1: Introduction

V and T are
constant
’

The pressure exerted by one

gas in a mixture is
independent of the other
gases in the mixture. P1 P2 Ptotal = P1 + P2
n1 n2 ntotal = n1 + n2
IN GENERAL: Ptotal = P1 + P2 + ……+ Pn
= (n1 + n2 + ……+ nn) RT/V
ntotal = n1 + n2 + ……+ nn
CHEM 2011
Consider a case in which two gases, A and B, are
CH 1: Introduction
in a container of volume V.

’ nART
PA = nA is the number of moles of A
V
nBRT nB is the number of moles of B
PB =
V
nA nB
PT = PA + PB XA = XB =
nA + nB nA + nB

PA = XA Ptotal PB = XB Ptotal

n
Pi = Xi Ptotal mole fraction (Xi) = i
ntotal
not just for gases
CHEM 2011
CH 1: Introduction

Consider the composite system, ntot = nHe + nNe + nXe = 0.464 mol
which is held at 298 K, shown
below. Assume ideal gas
behaviour, calculate the total PV (1.50 bar )  (2.00 L )
nHe = = = 0.121 mol
pressure, and the partial pressure R T (8.314  10 L bar K mol ) (298 K )
−2 −1 −1

of each component if the barriers

separating the compartments are PV (2.50 bar )  (3.00 L )
nNe = = = 0.303 mol
removed. Assume that the volume R T (8.314  10 L bar K mol ) (298 K )
−2 −1 −1

of the barriers is negligible. PV (1.00 bar )  (1.00 L )

nXe = = = 0.0403 mol
R T (8.314  10−2 L bar K −1 mol−1 ) (298 K )
CHEM 2011
CH 1: Introduction
MOLE FRACTIONS: nHe 0.121
He = = = 0.261
ntot 0.464
n 0.303
Ne = Ne = = 0.653
ntot 0.464
n 0.0403
 Xe = Xe = = 0.0860
ntot 0.464

TOTAL PRESSURE:
(nHe + nNe + nXe )RT (0.464 mol)  (8.314  10−2 L bar K −1 mol−1 ) (298 K )
Ptot = = = 1.92 bar
Vtot (6.00 L )

PARTIAL PRESSURES:
PHe = HeP = 0.261  1.92 bar = 0.501 bar
PNe = NeP = 0.653  1.92 bar = 1.25 bar
PXe = XeP = 0.08060  1.92 bar = 0.165 bar
CHEM 2011 a) Write a balanced equation for formation of SO3 from SO2 and oxygen.
CH 1: Introduction

b) At 310 K and 70 mbar, if 310 mL of O2 reacts with 568 mL of SO2, determine the
limiting reagent and the theoretical yield of the product, SO3?

c) If after the experiment, 420 mL of SO3 was collected, what is the percent yield?
CHEM 2011 d) In another experiment, an atmospheric chemist studying the pollutant SO 2
CH 1: Introduction places a mixture of SO2 and O2 in a 2.00-L container at 800 K and 1.90 atm.
When the reaction occurs, gaseous SO3 forms, and the pressure falls to 1.65 atm.
How many moles of SO3 form?

e) What is the mole fraction of SO3 in the final gas mixture?

CHEM 2011
CH 1: Introduction POSTULATES
1. Gas consists of tiny particles (atoms or molecules)
moving completely randomly
2. Volume of particles is negligible compared to total
volume occupied by gas (i.e. large separation
between individual gas molecules)
3. No attractive or repulsive forces between particles.
4. Gas molecules collide with one another (and other
things) without energy loss (elastic collisions)

The assumptions made in the kinetic-

molecular model break down at 5. The average kinetic energy of gas molecules is
proportional to temperature (Note: KE = ½mv2)
high pressure and/or low temperature.
CHEM 2011
CH 1: Introduction 1. Effect of size

• The gas laws were obtained
from experiments performed
under “normal” conditions of
temperature and pressure
(i.e. near STP)
Although it was assumed in KMT that gas particles occupy
very little space, their size does become more significant at
higher pressures.
2. Effect of intermolecular forces

• Under more extreme

conditions we get deviations
from the ideal gas law.
When particles are found at small separations,
intermolecular forces have to be taken into account.
CHEM 2011
CH 1: Introduction

molecular
volume

total
volume

At higher pressures, the gas particles

occupy a significant portion of the gas
volume.
The free volume (the one they can travel
through) is reduced from the measured “free” PV=nRT
total volume V to an extent proportional to volume
the number of molecules present and the
volume they each exclude. “free” volume

“FREE” VOLUME = total volume - molecular volume

CHEM 2011
CH 1: Introduction
Ordinary pressure:
molecules volume negligible
“free” volume ≈ total volume (measured)

High pressure:
Modelling the relationship by taking the
volume of molecules significant
volume effect into account:
“free” volume ≈ total volume (measured)
IDEAL GAS: V
REAL GAS: V - nb

b is a constant that depends upon the gas

𝒏𝑹𝑻
(𝐕 − 𝐧𝐛) =
𝑷
“FREE” VOLUME = total volume - molecular volume
CHEM 2011
CH 1: Introduction

• At higher temperatures and lower pressures

(even at STP), attractive forces between gas
particles are very weak relative to their kinetic
energy so these attractive forces have an
insignificant effect on their collisions.
• However, at lower temperatures the kinetic
energy of the gas particles decreases and the
weak attractions between them become more
significant.
LOW PRESSURE HIGH PRESSURE
CHEM 2011
CH 1: Introduction

Modelling the relationship by taking the effects

of intermolecular forces into account:
IDEAL GAS: P
P reduction
(red. in collision frequency/unit area) ∝ n/V
(red. in average force/collision) ∝ n/V
𝑛 2
REAL GAS: 𝐏 + 𝐚
𝑉
LOW PRESSURE HIGH PRESSURE
a is a constant that depends upon the gas
CHEM 2011
CH 1: Introduction

𝑛 2
𝑃+𝑎 × 𝑉 − 𝑛𝑏 = 𝑛𝑅𝑇
𝑉
Correction for Correction for
intermolecular forces particle size
Combining the effects of particle volume and
intermolecular forces
The van der Waals constants depend
𝑛 2 Gas a (L2·atm)/mol2) b (L/mol)
on the nature of the gas
REAL GAS: 𝐏 + 𝐚 He 0.03410 0.0238
𝑉
Ne 0.205 0.0167
REAL GAS: V - nb Ar 1.337 0.032
H2 0.2420 0.0265
yields the van der Waals equation which can N2 1.352 0.0387
be used to calculate the properties of a gas O2 1.364 0.0319
under non-ideal conditions (e.g. high P, low T). Cl2 6.260 0.0542
A gas that does not obey the ideal gas law is NH3 4.170 0.0371
known as a real gas. CH4 2.273 0.0430
CO2 3.610 0.0429
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CH 1: Introduction

For an ideal gas, PV = nRT n = PV/RT = 1 (for 1 mole)

For real gases, the ratio PV/RT, is greater or less than 1. PV/RT = 1

POSITIVE DEVIATIONS
due to the molecules having size and is quantified
by the “b” factor. (i.e. Vreal > Videal)

NEGATIVE DEVIATIONS
due to the molecules having intermolecular forces All gases display positive deviations at
and is quantified by the “a” factor. (i.e. Preal < Pideal) high enough pressures
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CH 1: Introduction

Gas a (L2·atm)/mol2) b (L/mol)

He 0.03410 0.0238
Ne 0.205 0.0167
Ar 1.337 0.032
Kr 2.349 0.0398
H2 0.2420 0.0265
COMPARISON
N2 1.352 0.0387

What contributes to the O2 1.364 0.0319

different shapes of curves Cl2 6.260 0.0542
observed for He and CO2?
NH3 4.170 0.0371
PV/RT = 1
CH4 2.273 0.0430
CO2 3.610 0.0429
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CH 1: Introduction
A graph of PV/RT vs. P for a series of real gases is shown below
Which temperature conditions (high or low) will result in the greatest
deviation at point X?

A) High temperature
B) Low temperature
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CH 1: Introduction

1. r < rV=0 , E > 0, repulsion

P is higher than calculated using ideal gas law.

2. rV=0 < r < rtransition , E < 0 , attraction

P is lower than calculated using ideal gas law.

3. r > rtransition , E = 0, no interaction

1 2 3
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CH 1: Introduction
Considering the potential energy of interaction of two
molecules or atoms, at which point, A, B, C or D, does
repulsion dominate over attraction?

D
A) A
B) B
C) C C

D) D

B
CHEM 2011
To synthesize ammonia using the Haber process, 2000 moles of nitrogen, N 2,
CH 1: Introduction
are heated in a 800-L vessel to 625 °C. Calculate the pressure of the gas if
nitrogen behaves (a) as an ideal gas and (b) as a van der Waals gas .
Comment on the results.

GIVEN Gas a (L2·atm)/mol2) b (L/mol)

N2 1.35 0.0386
n = 2000 moles
V = 800 L
T = 625 °C = (625 +273) K = 898 K
P=?
𝐿𝑎𝑡𝑚
𝑛𝑅𝑇 (2000 𝑚𝑜𝑙)(0.08206 )(898 𝐾)
𝑚𝑜𝑙𝐾
𝑷𝒊𝒅𝒆𝒂𝒍 = = = 184 atm
𝑉 800 𝐿

𝑛𝑅𝑇 𝑎𝑛2 (2000 𝑚𝑜𝑙)(0.08206

𝐿𝑎𝑡𝑚
)(898 𝐾) (1.35 𝑎𝑡𝑚 𝐿2 𝑚𝑜𝑙−2 )(2000 𝑚𝑜𝑙)2
𝑃= − 2 𝑷𝑽𝒅𝑾 = 𝑚𝑜𝑙𝐾
− = 195 atm
𝑉 − 𝑛𝑏 𝑉 800 𝐿 −(2000 𝑚𝑜𝑙 × 0.0386 𝐿 𝑚𝑜𝑙 −1 ) (800 𝐿)2

Pressure of the real gas calculation is higher than that of the ideal gas.
Repulsive interactions are more dominant.
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CH 1: Introduction