CHEM 155: BASIC PHYSICAL CHEMISTRY I

 Paradigm Shift in our conception

 Physical Chemistry and its Problems of Primary Concern
 Structure of Science and its Classification
 Theory Development: Concepts, Construct, Relationship,
Proposition, Laws, Hypothesis and Models.
 States of Matter I: Classification, Structure and Properties of
Matter, System & State Variables and Equation of State
 Thermodynamics I: First Law, Heat capacity, Enthalpy and
thermochemistry.
 Chemical Kinetics I: Elementary Chemical Kinetics, Basic Laws,
Effects of Temperature and the Arrhenius equation.
MATTER

 States of Matter, Structure (the way something is put

together) and Property.
 State and Variables of a System
 Equation of State.
 Gas Laws
 Kinetic theory of Gases
 Real Gases

Evans Adei CHEM 155

States of Matter
Matter – Definition:
 Aggregation of atoms/ions/molecules which come within the
scope of human experience i.e. any substance that has mass
and occupies space.
States of Matter:
 Matter exists in one of the following six states due to the
energy of its particles: Gaseous, Liquid, Solid, Plasma, Bose-
Einstein and Filament. The states of matter are also known as
phases of matter or states of aggregation.
 The division of matter into states is not always simple. How,
for example, should chocolate spread be considered. Some
scientists beleive that the so called colloids should be
considered.
Evans Adei CHEM 155
Six States of Matter

0 1 2 3 4 5
Name : Bose-Einstein Solid Liquid Gaseous Plasma Filament

Energy : ̃~zero <crystal <attract. <attract. <105 eV <1026 eV

Character : non-thermal thermal Thermal thermal thermal non-
thermal
Particle no motion Particles move in all three dimensions motion in
motion only one
direction

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State Property determined by Structure

Gas (simplest  Kinetic energy is more important  Collection of particles in continuous

state of matter) than potential energy. random chaotic motion.
 Intermolecularforce are weak.  Has no well-defined surface.
 No limit on extent of space or
volume it can occupy.
Liquid  Potential energy is more important  No long-range order but vestiges of
than kinetic energy. crystal lattice structure at short
 Intermolecular forces strong range.
 Has a surface and place a limit on
the extent of space or volume it can
occupy.
Solid  Potential energy is more important Generally possesses crystal lattice
than kinetic energy. structure –well defined shape
 Intermolecular force strong NB. Glass and solids exists as amorphous
solids.

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Thermodynamic System and Surrounding

 A ( thermodynamic) system is that part of the physical

universe that is separated from the rest of the universe
by a real or imaginary boundaries for consideration or
discussion.
 The part of the universe outside the boundary of the
system is referred to as surroundings i.e. where we
make our observations.
 Boundaries are of four types: fixed, moveable, real,
and imaginary.
 For closed systems, boundaries are real while for open
system boundaries are often imaginary

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Possible exchange between a system and its surroundings
a: system with diathermal walls.
b: System with adiabatic walls.

Exchange with the surrounding

Matter Heat Work
Isolated No No No
Closed No Yesa Yes
Nob
Open Yes Yes Yes

Evans Adei CHEM 155

PROPERTY
 A property is an essential or distinctive attribute
(quality) of something or a quality or characteristics
that something has.

 A property cannot be a function of the past history

(previous conditions under which it has existed) of a
system ; it depends only on the conditions at the
time of consideration

Evans Adei CHEM 155

 Description of State of matter

Extensive – Dependent on Size

Thermodynamics or e.g., m, n V,

Macrostate State Variables

Macroscopic Bulk

Intensive – Independent on Size

e.g., P, ρ, T

States of Matter

Nuclei

Micro or Atomic Variables

Microscopic State

Electronic

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Thermodynamic & Steady State Equilibria

Thermodynamic equilibrium
Properties of state are independent of time and there is no
flow of mass or energy.
Steady state equilibria
 When there is a flow of matter or energy through a system,
and yet no change of properties

Homogenous and Heterogenous systems

 A system is homogeneous if its properties are uniform
throughout and consists of a single phase or physical state.
 A system is heterogeneous if it contains more than one phase

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State function, Thermodynamic Property or
Property of State, State Variables

 State Function : Any system property (measurable

physical characteristic of a system, independent of how)
determined exclusively by the values of the initial and
final states. Examples are U, H, A, T, P, V etc.
 Path Function : Relate to the preparation of the state.
Examples, energy transfered as heat and work that is
done in preparing a state.
 Thermodynamic leads to the definition of additional
properties that can also be used to describe the states
of a system, and are themselves state variables. A, G, ..
Evans Adei CHEM 155
The internal energy is symbolically expressed as U(S, V, N), where S, V and N are
referred to as the natural variables of internal energy U.

The intensive properties of a system ; T, P and µ can be obtained by taking derivatives of

the extensive property U with respect to other extensive properties

𝜕𝑈 𝜕𝑈 𝜕𝑈
T= 𝜕𝑆
V,Nj P= 𝜕𝑉
S,Nj μ= 𝜕𝑁𝑗
S,V, Ni

The internal energy (U) and other thermodynamic properties defined (using Legendre
transformation) starting with the internal energy are referred to as Thermodynamic
Potentials : Enthalpy, H(S, P, N) ; Helmholz, A(T, V, N); and Gibbs, G(T,P,N). Where U,
H, A, and G contain the same information.

Evans Adei CHEM 155

EQUATIONS OF STATE
 The important idea that a system’s behaviour can be
described and predicted mathematically is expressed for
gaseous (simplest form of matter), liquid and solid systems
by saying that P is a function of T, V and n, denoted by
P = f(T,V, n) (1)
 The pressure P, is the dependent variable and there are
three independent variables, T, V and n. The letter f stands
for the functional relationship.
 Eqn (1) – Phenomenogically summarizes empirical
observation called laws or rules i.e. reflect some aspect of
the behaviour of nature and must therefore be correct
(within limits of experimental error).
Evans Adei CHEM 155
EQUATIONS OF STATE
 A state function is a concept related to an equation
of state ; it is a mathematical expression for a
property in terms of values of their properties used
to specify the state of a system.
 The equations of state for real systems ordinarily
obtained are approximate.
 The equation of state of most substances are not
known, so in general mathematical relation between
the four properties that defines a state cannot be
written down.

Evans Adei CHEM 155

Since Boyle’s law is applicable only at constant temperature and since Charles law is applicable
only at constant pressure, it is not immediately clear that the combination of the two laws is
justified. It follows from these laws that for a given mass of gas the volume is a function of the
pressure and the absolute temperature or

𝑉 = 𝑓 𝑃, 𝑇 (1)

𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑃 + 𝑑𝑇 (2)
𝜕𝑃 𝑇 𝜕𝑇 𝑃

1 𝑘1
𝑉𝛼 and 𝑉𝛼 ( T is constant) Boyles Law
𝑃 𝑃

𝜕𝑉 𝑘 𝑃𝑉 𝑉
= - 𝑃12 = - =-𝑃 (3)
𝜕𝑃 𝑇 𝑃

Also

𝑉 𝛼 𝑇 and 𝑉 = 𝑘2 𝑇 ( P is constant) Charles Law

𝜕𝑉 𝑉
= 𝑘2 = (4)
𝜕𝑇 𝑃 𝑇

Evans Adei CHEM 155

Substituting (3) and (4) into (2)

𝑉 𝑉
𝑑𝑉 = − 𝑑𝑃 + 𝑑𝑇
𝑃 𝑇
𝑑𝑉 𝑑𝑃 𝑑𝑇
𝑉
+ 𝑃
= 𝑇
(5)

Integrating (5)

ln 𝑉 + ln 𝑃 = ln 𝑇 + ln 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

PV = kT

For the special case in which only one mole of gas is considered,

k = R; R is called the molar gas constant defined by R = NAk = 8.31145Jk-1mol-1

Then, for n moles of gas

PV = nNAkT = nRT (Ideal or perfect gas law)

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REPORTING DATA
 Two sets of conditions are currently used as standard
values for reporting data:

T P Vm

STP (Standard temp. and pressure) 0 oC 1 atm 22.414L/mo l

SATP (Standard ambient T and P 25oC 105Pa or 1 bar 24.789 L/mol

R = PV/nT = [(1.00 atm)(22.4 L)]/[(1.00 mol.)(273 K)

= [(0.0821 L.atm)(101.32J)]/[(mol. K)(1 L. atm)]
= 8.314 J/mol. K

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PARTIAL PRESSURES AND MOLE FRACTIONS

The mole fraction (XJ) of J in a mixture is the amounts of J molecules present n J,

expressed as a fraction of the total amount of molecules (n) in the sample.

XJ = nJ/n (where n = nA + nB +…) (1)

Whatever the composition of the mixture,

XA + XB +…………. = 1 (2)

nA/n + nB/n + nC/n +…….. = 1

The partial pressure of a gas is the pressure, which a gas would exert at the same
temperature if it were alone in the container. The partial pressure PJ of a gas in a
mixture (any gas, not just a perfect gas) is:

PJ = XJP ………………………… (3)

It follows from (2)

XAP + XBP +……. (XA + XB+…….)P = P

Therefore P = PA + PB + ……….. (Dalton’s Law)

Evans Adei CHEM 155

The internal energy is symbolically expressed as U(S, V, N), where S, V and N are
referred to as the natural variables of internal energy U.

The intensive properties of a system ; T, P and µ can be obtained by taking derivatives of

the extensive property U with respect to other extensive properties

𝜕𝑈 𝜕𝑈 𝜕𝑈
T= 𝜕𝑆
V,Nj P= 𝜕𝑉
S,Nj μ= 𝜕𝑁𝑗
S,V, Ni

The internal energy (U) and other thermodynamic properties defined (using Legendre
transformation) starting with the internal energy are referred to as Thermodynamic
Potentials : Enthalpy, H(S, P, N) ; Helmholz, A(T, V, N); and Gibbs, G(T,P,N). Where U,
H, A, and G contain the same information.

Evans Adei CHEM 155

The internal energy is symbolically expressed as U(S, V, N), where S, V and N are
referred to as the natural variables of internal energy U.

The intensive properties of a system ; T, P and µ can be obtained by taking derivatives of

the extensive property U with respect to other extensive properties

T= V,Nj P= S,Nj μ= S,V, Ni

The internal energy (U) and other thermodynamic properties defined (using Legendre
transformation) starting with the internal energy are referred to as Thermodynamic
Potentials : Enthalpy, H(S, P, N) ; Helmholz, A(T, V, N); and Gibbs, G(T,P,N). Where U,
H, A, and G contain the same information.

Evans Adei CHEM 155

PARTIAL PRESSURES AND MOLE FRACTIONS

 The pressure exerted by a mixture of perfect gases is

the sum of the pressure exerted by the individual gases
occupying the same volume alone.
P = nRT/V and XJ = nJ/n = PJ/P

 PJ = (nJ/n) (nRT/V) = nJRT/V

 It is important to remember that the partial pressure is

defined by PJ = XJP for any gas but is equal to the
pressure that it would exert alone only in the case of a
perfect gas (no interaction between particles is a
perfect gas)
Evans Adei CHEM 155
THE KINETIC THEORY OF GASES
The kinetic theory is concerned with understanding the behavior of gases in terms of
molecular motion. Thus after describing the phenomenological equation of gases
there is the need for a quantitative theory which permits the various laws of
gaseous behaviour to be coordinated.
 The kinetic theory of gases is based on five assumptions.

 The gas consists of molecules of mass m and diameter d in ceaseless random motion.

 The size of the molecules is negligible (their diameters are much smaller than the
average distance traveled between collisions)
 The molecules do not interact except that they make perfectly elastic collisions (i.e.
the translation KE of a molecule is the same before and after a collision, no energy
is transferred to its internal moles of motion) when the separation of their centers is
equal to d. Thus there is no potential energy of interaction between the particles,
i.e. their energy is independent of their separation.
ET = EKE + EPE
= EKE, (EPE = 0 ; only translational energy is possessed by gas)
 The KE of the gas is directly proportional to the temperature.

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Qualitative Conclusions of Continuous Chaotic Motion

The continuous chaotic motion is in agreement with

observations:
 Elastic impacts on the vessel supposed to be
responsible for the pressure exerted by the gas.
 At constant volume an increase in temperature

results in more vigorous movement with consequent

increase in pressure.
 Decrease in volume increases elastic impacts on the
vessel and increase the pressure.
Evans Adei CHEM 155
Quantitative Conclusions

It is more important however, to see if the theory can

predict quantitatively the behaviour of gases:
 To calculate the pressure of the gas, we need to
calculate the force exerted by the molecules per unit
area of wall as they collide with it.
 That force is calculated using Newton’s 2
nd Law of

motion i.e. Force = rate of change of linear momentum.

 Computation of change in momentum per unit area
leads to
 PV = (1/3) nMc
2 = (1/3)Nmc2 (1)
Where M is the molar mass and c is the root- mean square speed (rms speed) of the molecules.

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Quantitative Conclusions
PV = (1/3) nMc2 = (1/3)Nmc2 (1)
Equation (1) has relation similar to PV = nRT.
 In equation (1) if the rms speed of the molecules depend only on the
temperature, then at constant temperature then,
 PV = constant (which is the Boyle’s law) (2)
This conclusion is a major success of the kinetic model, for from model a result
has been successfully derived which is valid experimentally.
 From equation (1), if a gas is at constant temperature and pressure, (V/n)T,P
is constant, which is Avogadro’s law; equal volume of gases at same
temperature and pressure contain the same number of molecules.
 For a gas at constant pressure,

 (c2)1/2  [V/(Nm)]1/2,

or the rate of effusion R α 1/D1/2 which is Graham’s law.

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 EQUIPARTITION
The total kinetic energy (transitional energy) E KE, of 1 mole of molecules is NA times the
average energy per molecule, that is
EKE = NAεKE = ( ½)NAmc2
Hence EKE = (½)Mc2 (3)
But PV = (1/3)nMc2 (4)
From (3) 2EKE = Mc2 (5)
Substituting (5) into (4)
PV = (1/3) n.2EkE = (2/3)nEKE = nRT (6)
therefore EKE = (3/2)RT (7)
Equation (7) shows that the Kinetic energy of an ideal gas is directly proportional to the
Kelvin temperature. Interpretation of absolute zero by kinetic theory is that the complete
cessation of all molecular motion contrary to quantum mechanics stipulation.

Since the only energy the gas possesses is translational (because the collision is elastic
Epotential = 0) the degrees of freedom (x, y. z) each translational degree of freedom has ½
RT (per mole). This is a special case of a more general theorem known as Principle of
Evans Adei CHEM 155
Equipartition of Energy.
 MOLECULAR SPEEDS
 The ability of the kinetic theory to account for Boyle’s Law suggests that it is a
valid model of perfect gas behaviour.

 We thus take a major step.

If PV = 1/3 nMc2
is to be precisely the equation of state of a perfect gas then the RHS must be equal to
nRT
PV = 1/3 nMc 2 = nRT

c = (3RT/M)1/2
 The root mean square speed of the molecules of a gas is proportional to the
square root of the temperature and inversely proportional to the square root of
the molar mass.
1/2
i.e. c α (T/M)
 The higher the temperature, the faster the molecules travel and, at a given
temperature, heavy molecules travel more slowly than light molecules.
Evans Adei CHEM 155
Maxwell Distribution of Molecular Speeds

 The chaotic continuous motion of molecules in a gas

 leads to numerous collisions with consequent redistributn
of molecular speeds of individual molecules that span a
wide range.
 The velocity of a molecule changes after a span of
even less than 10-9 seconds, thus making it difficult to
known the speed of individual molecules.
 However, there must be a fraction of the total number
of molecules that have a particular velocity at any time.
 This fraction was obtained theoretically by Maxwell
and Boltzman by utilizing probability considerations.

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 Maxwell Distribution of Molecular Speeds
According to Maxwell, the fraction f of molecules that has a speed in a narrow range s
to s + Δs is

Maxwell equation is a particular case of a general expression which finds application in

many aspects of physical chemistry. The expression is known as Boltzman’s
distribution (probability distribution). The probability distribution for molecular states in
a dilute gas is:

This has a number of important properties

 States of higher energy are less probable than state of lower energy.
 At higher temps, the different in population between states of high energy and
states of low energy decreases, until, as T approaches infinity, all states
approach equal probability.
 As T approaches zero on the Kelvin scale, only the states of lowest energy are
populated. Evans Adei CHEM 155
 Maxwell Distribution of Molecular Speeds

On dividing both sides of equation (1) by ds, we have

The expression gives the probability P of finding the molecules with the velocity

s as equation (1) and (2) are used forms of the equation for the Maxwell’s law of
distribution of velocities.

Evans Adei CHEM 155