Chem 332b/L

Physical Chemistry for Chemical

Engineers 1

Introduction

What is Physical Chemistry?

The term "physical chemistry" was coined byMikhail Lomonosovin
1752, when he presented a lecture course entitled "A Course in True
Physical Chemistry" (Russian: )
before the students ofPetersburg University.[9]In the preamble to
these lectures he gives definition: "Physical chemistry is the science
that must explain under provisions of physical experiments the
reason for what is happening in complex bodies through chemical
operations"

INTRODUCTION TO PHYSICAL CHEMISTRY

PHYSICAL CHEMISTRY

the branch of science that is concerned

with the physical principles that underlie
chemistry
seeks to account for the structure of
matter and the changes it undergoes in
terms of fundamental concepts such as
atoms, electrons, and energy.
provides the basic framework for all
other branches- inorganic, organic,
biochemistry, engineering

provides the basis of modern methods of nalysis, the

determination of structure, and the elucidation of the
manner by which chemical reaction occur.

it establishes the link between the properties of bulk matter

and the behavior of particles- atoms, ions, or molecules-of
which it is composed.

In general sense, physical chemistryis defined as the study

of macroscopic, atomic, subatomic, and particulate
phenomena in chemical systems in terms of laws and
concepts ofphysics. It applies the principles, practices and
concepts ofphysicssuch
asmotion,energy,force,time,thermodynamics,quantum
chemistry,statistical mechanicsanddynamics,equilibrium.

States of Matter and the properties of Gases

the broadest classification of bulk matter is into one of the

three physical states- solid, liquid, and gas

the three states of matter can be recognized by their behavior

when they are enclosed in a container:
solid- retains its shape independent of the shape of the
container it contains
liquid- a fluid state of matter that possesses a well-defined
surface and (in a gravitational fields) fills the lower part of the
container it occupies
gas- a fluid state of matter that fills the container it occupies

The essential difference

between the three states
of matter comes down to
the freedom of particles
to move past the other.

If the particles are widely separated on average, there is

hardly any restriction on their motion, and the substance is
a gas.

If the particles interact so strongly with each other that they

are locked together, then the substance is a solid.

If the particles have an intermediate mobility between

these extremes, the nthe substance is a liquid.

In this chapter, we'll see how to describe gases, the simplest

of these three states of matter.Although gases are simpleboth to describe and in terms of their internal structurethey are of immense importance.

The description of States

of Matter

the term 'state' has many different meanings in

chemistry

e.g. 'the states of matter' - solid state, liquid

state, gaseous state

by state we shall mean a particular condition of

a sample of matter that is described in terms of
the volume, pressure temperature and amount
of substance present.

Volume
the volume of a sample is a measure of the
space it occupies
Pressure, p, we mean force ddivided by the
area on which force is exerted.
- pressure is measured in the unit called pascal,
Pa:

p= F/A

Pressure Units and Conversion Factors

SI: pascal ( Pa)

1 Pa= 1 N m -2

bar

1 bar= 10 5 Pa

atmosphere

1 atm = 101.325 kPa

torr

760 torr= 1 atm

1 Torr= 133.32 Pa

atmospheric pressure (a property that varies with altitude

and the weather)is measured in barometer-- which
isinvented by Torricelli.
p= gph
h- height of the column
p- (rho) density of the liquid

manometer - a pressure gauge that measures pressure of a

gas inside a container

Temperature

Temperature, T, of an object is a property that

determines in which direction energy will flow
when it is in contact with another object

energy (heat) flows from the higher

temperature to the lower temperature.

when the two bodies have the same

tmeprature, there is no net flow of heat
between them. These bodies are in thermal
equilibrium

Kelvin scale- more convenient to use in many scientific applications.

Temperature Conversion:

Celsius
[C]=([F]32)59
Kelvin
[K]= 59([F]+460)
Rankine
[R]=[F]+460

For temperature intervals rather than specific temperatures,

1 F = 1 R
and
1 F = 59 C

Amount of Substance

mass, m, of an object is a measure of the

quantity of matter it contains.
SI unit of mass is the kilogram (kg), with 1 kg
currently defined as the mass of a certain block
of platinum-iridium alloy preserved at Sevres,
outside Paris.
In Chemistry, where the focus is on the
behavior of atoms, it is usually more useful to
know the number of atoms, molecules, or ions
in a sample rather than the mass of a sample

1 mole of particle is equal to the number of atoms in exactly 12 g of

Carbon-12.

In practice,

Avogadro constant, NA=

1 mole= 6.02214 x 10
6.02214 x 10

23

particles

23

n = number of particles/number of particles per

mole
= N/NA

Ex. : 8.8 x 10

22

Cu atoms corresponds to 0.15 mol

1.8 mol Xe contains how many Xe atoms?

molar mass, M, is the massper mole of substance

Ex. the molar mass of C atoms is 12.01 g mol-1

the molar mass of an element means the mass per mole of

its atoms.

the molar mass of a compouund is the molar mass of its

molecules, or in the case of ionic compounds, the mass per
mole of its formula units.

a formula unit is the physical entity corresponding to a specific

chemical formula
Ex. the formula unit for Na2SO4 consists of two Na + ions and one
SO4 2- ion
n = mass of sample/molar mass
= m/M

Find the amount of S atoms present in 45.6 g

of S.

Ex.

Note: the former names for molar mass were

atomic weight, for the mass per mole of
atoms, and molecular weight, for the mass
per molecules, both terms are still far from
dead.

Equations of State

The state of any sample of substance can be

specified by giving the values of the following
properties:

V, the volume the sample occupies

p, its pressure

T, its temperature

n, the amount of substance it cointains

the four quantities are not independent of one another

if we select the amount, the volume , and the temeprature, ,

we have to accept a particular pressure

the substance obeys an equation of state, an equation that

relates one of the four properties

the general form of an equation of state is

p= f (T, V, n)

The Perfect Gas Equation of

State
Boyle's and his successor's experiments led to the
formulation of the following perfect gas
equation of state:
pV = nRT
where R, known as the gas constant, is a constant
with the same value for all gases.
R= 8.3145 kPa L K-1 mol

-1

the perfect gas equation of state- the perfect gas law- is socalled because it is an idealization of the equations of state
that gases actually obey.

it is found that all gases obey the equation more closely as the
pressure is reduced toward zero

the equation is an example of a limiting law, a law that is not

obeyed exactly by an actual gas, but becomes increasingly
valid as the pressure is reduced and is obeyed exactly in the
limit of zero pressure.

Perfect Gas
- a hypothetical fluid that obeys the equation (the perfect gas
equation of state) at any pressure
Real Gas
-an actual gas, which behaves more and more like a perfect
gas as its pressure is reduced, and behaves exactly like a
perfect gas when the pressure has been reduced to zero.

The perfect gas law summarizes three sets of observations :

Boyle's Law- at constant temperature the pressure of a fixed
amount of gas is inversely proprotional to its volume. When
nand t are constant, the perfect gas law becomes
pV= constant
hence,
p 1/V

Charles' Law:
the volume of a fixed amount of gas at
constant pressure is proportional to the
temperature, T.
when n and p areboth constant
V T
- Charles' Law indicates that there exists an
absolute zero of temperature, a
temperature below which it is impossible to
cool an object

Avogadro's Principle:
- At a given temperature and pressure, equal volumes of gas
contain the same number of molecules.
- if a sample of air at 100 kPa occupies 1.00 L at 300 K, and a
sample of pure carbon dioxide occupies the same volume
under the same conditions, then we can infer that both the
samples contain the same number of molecules
- the molar volume, Vm, of any substance (not just a gas) is
the volume it occupies per mole of molecules present in the
sample.
- Avogadro's principle implies that the molar volume of a gas
should be the same for all gases at the same temperature
and pressure.

Using the Perfect Gas Law :

The perfect gas law is used when we want to

predict the pressure of a gas given its
temperature, its chemical amount, and the
volume it occupies.
p= nRT/V

Predicting the pressure of a

sample of gas
1. What pressure is exerted by 4.5 g of oxygen gas
in a flask of volume 300 mL at 20 0C ?
2. Calculate the pressure exerted by 1.22 g of
carbon dioxide confined to a flask of volume
670 mL at 39 0C

In case, that a pressure is given under one set of

conditions , and we are asked to predict the
pressure of the same sample under a different
set of conditions, we can use the combined
gas equation .
p1V1/ T1 = p2V2/ T2

Ex.
What is the final volume of a sample of gas that
has been heated from 25 0 C to 1000 0 C and
its pressure increased from 10.0 kPa to 150.0
kPa, given that its initial volume was 15 mL?

The perfet gas law can also be used to

calculate the molar volume of perfect gas
at any temperature and pressure.
Vm = V/n
= (nRT/p)/n
= RT/p
standard ambient temperature and
pressure (SATP)
T= 25 0 C (more precisely, 298.15 K )
p= 100 kPA (1 bar)
Vm= 24.79 L mol-

Mixtures of Gases: partial

pressures
Dalton's Law:
'The pressure exerted by a mixture of perfect
gases is the sum of the pressures exerted by
the individual gases occupying the same
volume alone."

= pA + pB + pC...

total

where
- Dalton's law is strictly valid only for mixtures of
perfect gases ( or for real gases at such low
pressures that they are behaving perfectly)

-Mole fraction,XJ of a species J is the chemical

amount of J expressed as a fraction of the total
amount of molecules present in the sample.
xA= nA / (nA + nB + ....)
xA + xB = 1

Ex.
Calculate the mole fractions of N2, O2, and Ar in dry air at sea level,
given that 100.0g of air consists of 75.5 g of N2, 23.2 g of O2, and
1.3g of Ar.

partial pressure
pj

x jp

where:
pj - partial pressure of the species j
xj - mole fraction of species j
p - total pressure

Calculating partial pressures

Many environmental and biophysical arguments

depend on a knowledge of the composition of
the atmosphere, and in particular on the partial
pressures of its principal components. Given
that the composition of the sample of mass
100g of dry air at sea level is 75.5 g nitrogen,
23.2 g oxygen, and 1.3 g argon, what is the
partial pressure of each component at 100 kPa
total pressure?