Physical Chemistry is the study of the underlying physical

principles that govern the properties and behavior of chemical

systems
A chemical system can be studied by microscopic (based on
the concept of molecules and macroscopic (large-scale
properties of matter) viewpoints
Chemical Physics denotes those aspects of Physical Chemistry
that study phenomena at the molecular level.
Thermodynamics is a macroscopic science that studies the
interrelations of the various equilibrium properties in processes
Quantum Chemistry is the application of quantum mechanics
to atomic structure, molecular bonding and spectroscopy
Statistical Mechanics relates the macroscopic and molecular
levels of viewpoints
Kinetics is the study of rate processes (chemical reactions,
diffusion, flow of charge in an electrochemical cell
Pressure force divided by the area to which the force is applied
EXAMPLE: Find the pressure at the base of a column of liquid of
mass density and height h at the surface of the earth
Start with definitions: P = Force/Unit Area
= mass/volume
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Solution: volume of the column of liquid = A h

mass = A h
gravitational force = mg
pressure = h g this is the equation you need!
760 mmHg at 298.15 K exerts a pressure equal to:
13.591g cm-3 x (102 cm/m)3 x (10-3 kg/g) x 760 mm x (10-3 m/mm)
x9.81 m s-2 = 1.01325 x 105 kg m-1 s-2
Units of Pressure
Per definition pressure has dimensions of force divided by area and
in SI the units are N/m2, also called pascals (Pa)
1 Pa = 1 N/m2
1 torr = (13.591 g/cm3) (1 kg/103 g)(102 cm/m)3 (9.80665 m/s2)
(10-3 m) = 133.322 kg m-1 s-2 = 133.322 N/m2 = 133.322 Pa
1 atm = 760 torr = 1.01325 x 105 Pa
1 bar = 105 Pa = 0.986923 atm = 750.062 torr
Units of volume
cm3, dm3 , m3 and liters (L or l)
The liter was originally defined as the volume of 1000 g of water at
3.98oC and 1 atm. This made the liter equal to 1000.028 cm3 In
1964 the liter was redefined as exactly 1000 cm3.
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1 L = 1 dm3 = 1000 cm3

Why? 103 cm3 = 103(10-2 m)3 =10-3 m3 = (10-1 m)3 = 1 dm3
Temperature a property of a system. It tells us the direction of the
flow of energy
-thermal equilibrium
-diathermic wall
Extensive variable (extensive property): varies directly with the
mass. (n, V)
Intensive variable (intensive property): independent of the
amount of mass. (T, P)
GASES are the simplest state of matter
Completely fills any container it occupies
Pure gases (single component) or mixtures of components
The Ideal Gas
One experimental information that is very useful is that at a given
pressure and temperature, the molar volume V/n of a gas is
approximately the same regardless of the identity of the gas
Avogadros Principle - Equal volumes of gases at the same
pressure and temperature contain the same number of
molecules
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 Boyle-Mariotte Law
Robert Boyle (1662) and Edne Mariotte (1676)
PV = k at constant m and temperature
For a fixed amount of gas kept at a fixed temperature, P and V are
inversely proportional
Charles (1787): At a constant pressure the volume of a given
amount of gas is directly proportional to the absolute
temperature
V/T = k
Gay-Lussac (1802): for a fixed amount of gas and at constant
pressure the volume increases linearly with temperature during
a thermal expansion of the gas

The volume of a fixed amount of a gas at a fixed low pressure is

found to vary with temperature in a straight line and has the same
temperature intercept (-273.15 on the Celsius scale) regardless of
the gas or the pressure (only that P is low enough).
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This behavior defines a temperature scale called absolute

temperature, in which one Kelvin is the same temperature
increment as one Celsius and the offset is 273.15.
T (K) = t (oC) + 273.15
With a narrow range of temperature and pressure values, some
gases approximately obey a simple equation of state
Perfect Gas Equation or Ideal Gas Equation of State
V 1/P (constant T and n) (Boyle-Mariotte Law)
V T (constant P and n) (Charles Law)
V n (Avogadros principle)

nT
V P
nT
=R P
PV=nRT
In the limit P 0, all empirical gas behavior approach the ideal gas
equation of state.
Gas constant, R
8.20578 x 10-2 L atm K-1 mol-1
8.31451 x 10-2 L bar K-1 mol-1
8.31451 Pa m3 K-1 mol-1
8.31451 J K-1 mol-1
1.98722 cal K-1 mol-1
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Daltons Law (of partial pressures) (1801): the total pressure of a

gas mixture was the sum of the partial pressure of each gas.

Ptotal = P1 + P2 + P3 + ....... Pn
The Partial Pressure is defined as the pressure of a single gas in
the mixture as if that gas alone occupied the container.
Point to remember: Dalton maintained that since there was an
enormous amount of space between the gas molecules within the
mixture that the gas molecules did not have any influence on the
motion of other gas molecules, therefore the pressure of a gas
sample would be the same whether it was the only gas in the
container or if it were among other gases. This assumption that
molecules act independently of one another works fine as long as
there is a lot of space between gas molecules in the mixture and
the temperature is not too low. Lowering the temperature and/or
compressing the gas will upset that assumption.
EXAMPLE: If we have 2 moles of H2, 4 moles of O2, and 6 moles
of He in a 5 liter vessel at 27 C, determine the partial pressure of
each gas and the total pressure of the mixture.
Method 1: Using the ideal gas equation
1. Convert the temperature to Kelvin: K = 27 + 273 = 300 K
2. Using the PV = nRT equation determine P for H2:
P H2 = nRT / V = (2 moles H2) (0.821 liter-atm / mol-K) (300K)
/ 5 liters = 9.85 atm
Determine the partial pressure for the O2:
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PO2 = nRT / V = (4 moles O2)(0.0821liter-atm/mol-K) ( 300K)

/ 5 liters = 19.7 atm
Determine the partial pressure of He:
PHe = nRT / V= (6 moles He)( 0.0821 liter-atm /mol-K)(300 K)
/ 5 liters = 29.55 atm
3. Total pressure = PH2+PO2+PHe = 9.85+19.7+29.55 =59.1 atm
Method 2: Using the Mole Fraction Relationship
1. If one knows the moles or grams of each gas and the total
pressure, one can determine the Partial pressure of each gas with the
following formula:

P1 = X1 ( Ptotal) where X1 = mole fraction of the gas

2. Mole Fraction is defined as the moles of the gas divided by the
total moles of all the gases in the mixture:

X1= n1 / ntotal

Isotherms: P vs. V
Plots depicting Boyle-Mariotte Law: each plotted line corresponds
to a different temperature, and are known as isotherms
isotherm a mathematical curve that corresponds to a relation
between a set of two or more variables at constant temperature
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For plots of P vs. V, the isotherms are hyperbolas (i. e., plot of y
as function of x when xy = constant)
For plots of P vs. 1/ V, the isotherms are linear
Isotherms for an ideal gas:

isobar a mathematical curve that corresponds to a relation

between two or more variables at constant pressure
isochore a mathematical curve that corresponds to a relation
between two or more variables at constant volume

A few definitions
System - a thermodynamic system is that part of the physical
universe the properties of which are under investigation. The
system is confined to a definite place in space by the boundary
which separates it from the rest of the universe, the
surroundings.

 Open system transfer of matter between system and

surroundings can occur
Closed system no transfer of matter between system and
surroundings can occur
Isolated system does not interact in any way with the
surroundings
Boundaries between objects
1) Diathermic - heat flows between bodies. Change of state
occurs when bodies of different temperature are brought
into contact
2) Adiabatic - heat flows between bodies. No change of
state occurs when bodies of different temp brought into
contact
Properties the properties of a system are those physical
attributes that are perceived by the senses, or are made
perceptible by certain experimental methods of investigation
State of system a system is in a definite state when each of
its properties has a definite value

Equation of state of the system the mathematical

relationship between the values of the properties: mass,
volume, temperature, and pressure P = f (T,V,n)
,

P V = n R T (Ideal Gas Equation of State)

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Real Gases
Do not obey the perfect gas equation exactly. The deviations from
the law are particularly important at high pressures and low
temperatures, especially when the gas is on the point of condensing
to a liquid.
1) Repulsive forces important only when molecules are nearly in
contact, i.e. very high pressures
2) Gases at high pressures less compressible
3) Attractive forces operate at relatively long range (several molecular
diameters)
4) Gases at moderate pressures are more compressible since attractive
forces dominate

Molecular Interactions (between molecules in a gas or other phase

of matter) At low pressures, neither repulsive or attractive forces
dominate - ideal behavior

Potential Energy/Kinetic Energy

Potential energy curve describes how the potential energy
changes as a function of distance (sometimes also orientation)
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Isotherms of real gases

Compressibility factor or compression factor: measure of gas

deviation from ideality
Z = PVm /RT
For an ideal gas Z = 1 under all conditions of T and P
At very low pressures all the gases shown have Z = 1 and behave
near perfectly. At high pressures Z > 1 (more difficult to compress
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than a perfect gas, repulsive forces are dominant), at intermediate

pressures most of the gases have Z < 1 (attractive forces are
dominant and favor compression)
Virial Coefficients
General virial equation of state: Z = 1 + B/Vm+ C/Vm2 + D/Vm3 +

B, C, D, are called the second, third, fourth,virial coefficients

If enough terms are included, the general virial equation of state can
describe any observed P, V, T behavior

Typical variation of second and third virial coefficients with

temperature

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Consider,

PVm = RT(1 +

B C
+ 2 + ....)
Vm Vm

For a perfect gas: dZ / dP = 0 , because Z=1 at all pressures

For a real gas dZ / dP = B '+2 PC '+.... B' as P 0
However, B' is not necessarily zero and the slope of Z w/r/t P does
not approach 0. The properties of real gases do not coincide with
the ones of ideal gases even at very low pressures.
dZ
And d (1 / V ) B as Vm (corresponding to P 0)
m

The virial coefficients depend on temperature, so there exists a

temperature at which Z 1 with zero slope at low pressure or high
molar volume. This is called Boyle temperature (TB): at this
temperature the properties of the real gas coincide with the ones of
the ideal gas.

14

Variation of the compression factor, Z, with pressure at 0oC

(left) and for CH4 at several temperatures (right)

15

16

17

18

There is a certain maximum pressure, Pc (the critical pressure) and a

certain maximum temperature Tc (the critical temperature) at which
liquid and vapor can coexist. That, is liquid and vapor can coexist at
values below Pc and Tc, but at values above Pc and Tc only one
continuous fluid can exist.

Equations of State
van der Waals (1873)

nRT
n
) a ( ) 2 or
V nb
V
RT
a
P=(
) 2
or
Vm b Vm
V
a
Z =( m )
Vm b RTVm
P=(

Significance of b and a
b has units of volume/mole
accounts for molecular size and volume of the molecules themselves
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[the empty space between the molecules extrapolate to zero as the

temperature goes down as required by the ideal gas equation of
state]
a has units of P * (concentration)-2
it accounts for interaction between molecules which diminish the
pressure that would be exerted by completely independently moving
particles

Is van der Waals equation reliable to predict the behavior of real

gases?
One region where the van der Waals equation works well is for
temperatures that are slightly above the critical temperature Tc of a
substance

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The Features of van der Waals Equation

1. Perfect gas isotherms are obtained at high temperatures and
large molar volumes
RT
a
nRT
n
) 2 (b)
) a ( ) 2 (a) or , P = (
P=(
Vm b Vm
V nb
V
When T is so high RT is so large that the first term greatly
exceeds the second. If Vm is large then Vm - b Vm, then the
state equation reduces to
RT
P=
Vm , the perfect gas equation
2. Liquids and gases coexist when cohesive and dispersing
effects are in balance. This occurs when both terms at (b) have
similar magnitudes
3. The critical constants are related to the van der Waals
coefficients.
For T = Tc the calculated isotherms oscillate and each one
passes through a minimum followed by a maximum. These
exrema converge as T Tc and coincide at T = Tc. At the
critical point the curve has a flat inflection, which means that
the first and second derivatives are zero at the critical point.

dP
RT
2a
=
+
=0
dVm
(Vm b) 2 Vm3
d 2P
2 RT
6a
=

=0
2
3
4
dVm (Vm b) Vm

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Solving these two equations we get,

Vc = 3b

Zc =

Pc =

a
27b 2

PcVc 3
=
RTc 8

Tc =

8a
27 Rb

(GOOD FOR ALL GASES

a and b can be determined from the value of the critical constants.

The principle of corresponding states
The values of Pc , Tc and of the molar volume Vmc can be used to
reduce the equations of state of all gases so that they can all be
compared with one another in a reduced form of the equation of
state.
We define,
Reduced pressure: Pr = P/Pc
Reduced temperature: Tr = T/Tc
Reduced volume: Vr = V/Vc
Real gases at the same reduced volume and reduced temperature
exert the same reduced pressure
8Tr
3
Pr =
2
3Vr 1 Vr
approximation only
works best for spherical molecules
fails badly for non-spherical or polar molecules
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 Other equations of state: based on models for real gases as

well as cumulative data on gases
Redlich-Kwong (1949)

considerable improvement over other equations of the time.

relatively simple
superior to the van der Waals equation of state,
it performs poorly with respect to the liquid phase
23

 adequate for calculation of gas phase properties when

Dieterici

24