CHAPTER 1

Introduction to Physical Chemistry

Topics :
1. Overview of Physical Chemistry
2. Matter and Energy
3. The Properties of Gas
4. The Gas Laws
5. Spectroscopy Techniques

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Math Chemical Law of

methods Systems physics
 Reasoning chemical phenomena
 Predicting properties + reactions

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Chemical System Study

chemical Aggregation of - gas
bonding atoms/molecules
atoms molecules Bulk - liquid

- solid
Microscopic Macroscopic
Statistical Mechanics

Quantum Chemistry
Properties: Properties:
Molecular masses Entropy
Molecular geometries Internal energy
Intermolecular forces Heat capacity
Chemical reaction rate

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Physical Chemisty Fields

a) Quantum Chemistry
• application of quantum mechanics to atomic structure &
molecular bonding.
b) Statistical Mechanics
• deduce the macroscopic properties of matter from the
properties of molecules in a system.
c) Thermodynamics
• study of feasibility of chemical reactions, heat, work, and
energy changes involved during reaction.
d) Kinetics
• study of rate law, order and molecularity of a reaction,
diffusion rates in gasses.

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State of Matters
Physical
appearance State

specific shape Solid

specific density
Substances Liquid
variable shape
Gas
variable density

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Multiple Phases

 Pure component  Heterogeneous

one - multiphase mixtures multiple
component  Pure component  Homogenous component
- 1 phase mixtures

Single Phase

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Changing of State
Solid
ts, P = 1 atm tf, P = 1 atm

Gas Liquid
tb, P = 1 atm

tf = freezing/melting temperature
tb = boiling/condensing temperature
ts = sublimation temperature
temperature (t)
& are state’s variables or properties
pressure (P)
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Pressure (P):

Atmospheric Pressure is measured by the

level of Hg (mm or cm) in the glass tube.

Without air, the level of Hg in the glass

tube is equal to the level of Hg in the
tray at sea level.
The level of Hg is 760 mm or 76 cm at
sea level, so atmospheric pressure is
760 mm Hg (torr) = 1 atm = 1.013 bar
= 101.325 kPa 760 mm

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Temperature (T)
 is the measurement of HEAT
is a form of energy can be quoted
in Joules (J) or Calories.

Unit of temperature = ˚ C (Celsius), K (Kelvin)

T (K) = T (˚C) + 273.15
Kelvin also called “thermodynamic temperature’’
0 K = absolute temperature

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Quantifying Matter
• Substance: A pure form of matter
• Amount of substance: Reported in terms of moles.
1 mol of a substance contains as many entities as exactly 12 g of
carbon-12 (ca. 6.02 x 1023 atoms)
• Avogadro’s Number: NA = 6.02 x 1023 mol-1
• Extensive Property: Dependent upon the amount of matter in
the substance (e.g., mass & volume)
• Intensive Property: Independent of the amount of matter in a
substance (e.g., mass density, pressure and temperature)
• Molar Property: Xm, an extensive property divided by the
amount of substance, n: Xm = X/n
• Molar Concentration: “Molarity”= moles of solute dissolved in
liters of solution: 1.0 M = 1.0 mol L-1

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SI vs. Gaussian Units

Older literature sources and many Americans still use the
Gaussian system of units, so it is useful to understand the
relationship between the SI and Gaussian systems.
SI Units Gaussian Units
Name Symbol Name Symbol Conversion
meter m centimeter cm 0.01 m
kilogram kg gram g 0.001 kg
second s second s
ampere A biot Bi 10 A
kelvin K kelvin K
mole mol Mole mol
candela cd Stilb sb 104 cd m-2
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SI Derived Units
Derived quantity Name Symbol
volume cubic meter m3 or L or dm3
speed, velocity meter per second m/s
acceleration m. per s. squared m/s2 or m s-2
wave number reciprocal meter m-1
mass density kg per cubic m kg/m3 or kg m-3
frequency hertz Hz : s-1
force newton N : kg·m·s- 2
pressure, stress pascal Pa : N/m2 : kg·m-1·s-2
energy, work, heat joule J : N·m : kg·m2·s-2
power, radiant flux watt W : J/s : kg·m2·s-3
electric charge coulomb C : A·s
electric potential voltan V : W/A : kg·m2· s-3·A-1
magnetic field tesla T : A/m

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SI vs. Gaussian Derived Units

Many important units, some with special names and symbols,
can be derived from the SI base units:
Derived quantity Symbol Conversion
erg (energy) erg 1 erg = 10-7 J
dyne (force) dyn 1 dyn = 10-5 N
gauss (magnetic field) G, Gs 1 G = 10-4 T
Other units
calorie (energy, thermo) cal 1 cal = 4.184 J
calorie (food energy) Cal 1 Cal = 1 kcal = 4184 J
electron volt (energy)* eV 1 eV = 1.602 177 33 x 10-19J
micron (distance) μ 1 μ = 10-6 m = 1 μm
Angstrom (distance) Å 1 Å = 10-10 m

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Example :

−3 N
L⋅a t = m1 0 × 1
m3
.30× 1 1 02
3
m
= 1 0.3 1N ⋅ m

= 1 0.31J

g m go m l L o m l −L
3 g
⋅ = ⋅ ⋅ 3 ⋅ 3
= 1 3
0
m L o m l L 1o m c0l Lm c

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Pressure (P)
 force that exerts on unit area

F ( f o r) c
P =
A (a r ) e a
Unit of Pressure :
N Pound
2
(Pascal), 2
(psi)
m in

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Atmospheric pressure is the pressure causes

by mass of air exerting on ground.
1
Lower
2
Density of air

3
Higher

Gravitational force at higher altitude is less dense than at

lower altitude.
P@ 1 < P@ 2 < P@3
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Other Properties
- amount of substance (M) - volume (V)
- mass (m) - density (m/v = d) etc.
For pure substance, only T and P or T and V or P and V are
enough to specify a state. (P, V, T are related; by knowing
only 2 properties then the third will be known)
For mixture, the amount of substances must be specify
(T, P, n1, n2, ….)
 Intensive properties do not change when the amount of
substances change such as T, P, d….
 Extensive properties change when the amount of substances
change such as V, n, m…..
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Energy

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Contributions to Energy

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The Properties of Gases

a) The Perfect (Ideal) Gas
 Equation of state
 Gas laws
 Kinetic model of gases
b) Real Gases
 Molecular interactions
 Van der Waals equation
 Principle of corresponding states

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Phase of
Matter

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Perfect Gases
• We shall consider a hypothetical perfect or ideal gas,
which is a form of matter that completely fills any container.
• A perfect gas is pictured as a collection of molecules or atoms
which undergo continuous random motion (or Brownian
motion):
- The speeds of the particles increase as the
temp. is increased.
- The molecules are widely separated from
one to another, with only interactions being
with the side of the container & with other
molecules during infrequent collisions.
- The molecules are unaffected by
intermolecular forces
(e.g., dipole-dipole, van der Waals, etc.)
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Equation of state
 The equation of state of the system is the mathematical relationship
between the values of four properties (amount of substance, temperature,
volume, and pressure) of the gas.

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Pressure

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Pressure Exerted by Gases

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Measuring Pressure

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Temperature
The concept of temperature springs from the
observation that a change in physical state
(e.g., a change of volume) can occur when
two objects are in contact with one another.
The change in state can be interpreted as a
flow of energy as heat from one object to
another.
Diathermic boundary  a change of state is
observed when two objects at different
temperatures are brought into contact.
Adiabatic boundary  no change occurs even
though the two objects have different temperatures.

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Thermal Equilibrium
Thermal equilibrium is established if no change of state occurs
when two objects A to B are in contact through a diathermic
boundary.
Zeroth Law of Thermodynamics:
A If A is in thermal equilibrium with B,
and B is in thermal equilibrium with
C, then C is also in thermal
C B equilibrium with A.

The Zeroth Law justifies the concept of temperature and

the use of a thermometer for measuring the temperature.

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Thermometers and Temperature

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The Gas Laws

• Individual Gases :
 Boyle’s Law
 Charles’ Law
 Avogadro’s Law
• Perfect (Ideal) Gas Equation
• Mixtures of Gases :
• Dalton’s Law
• Mole Fractions
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Boyle’s Law

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Boyle’s Law
Boyle’s Law states that the volume of a fixed mass of
gas is inversely proportional to its pressure at constant
temperature.
1 1
Vα or P α
P V
P V = constant

P1 V1 = P 2 V 2

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Rationalizing Boyle’s Law

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Charles Law

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Gay-Lussac experiment

• Gay-Lussac measured the volume of fixed mass of gas under a

constant pressure and found that the volume was a linear
function of temperature.

V = a + b ×T
dV
V=
V0 + ( ) × T
dT

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Charles’ Law
Charles’ Law states that the volume of a fixed mass of
gas is directly proportional to its absolute temperature at
constant pressure.
V• T
V
or = constant
T

V1 V 2
=
T1 T 2

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Effects of Changing Temperature

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Rationalizing of Charles’ Law

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Avogadro’s Law
Avogadro’s Law states that equal volume of all gases,
measured at the same temperature & pressure, contain
the same number of molecules (the same number of
moles of gas).

n
n • V or = constant
V

n = no. of moles of gas

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Combination of Gas Laws

1
Hence, V • , V • T and V • n
P
nT
Therefore; V • Rearrangin g : PV • nT
P
So; PV = nRT Ideal Gas
(R = gas constant) Equation
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The Gas Constant

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For a fixed no. of moles of gas (n = constant):

PV P1V1 P2V2
= constant or = Combination of Boyle’s
T T1 T2 & Charles Laws……
At std temp & pressure (S.T.P.) : 1 mol of any gas occupies
22.4 dm3 at 273.15 K (0˚ C) & 101325 Pa (1 atm).
Molar vol. of gas, Vm = 22.4 dm3 mol-1 (or 22.4 L mol-1)

At std ambient temp & pressure (S.A.T.P.) : 1 mol of any

gas occupies 24.79 dm3 at 298.15 K (25˚ C) & 101325 Pa
(1 atm).
Molar vol. of gas, Vm = 24.79 dm3 mol-1 (or 24.79 L mol-1)

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John Dalton

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Dalton’s Law of Partial Pressure

State that in a mixture of gases that do not interact with
one another, the total pressure of the mixture is the sum
of the partial pressure of the constituent gases.

PT = PA + PB + PC + ..........
where PA, PB and PC = partial pressure of gas A, B and C
PT = total presure of the mixture

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Mole Fraction
PA = χA x PT
where χA = mole fraction of gas A in the mixture

nA
χA =
nT
nA = no. of moles of gas A in the mixture
nT = total no. of moles in the mixture

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Real Gases
Real gases do not obey the perfect gas law exactly. Deviations
from the law are particularly important at high pressures and
low temperatures, especially when a gas is on the point of
condensing to liquid.

Molecular Interactions
 Real gases show deviations from the perfect gas law
because molecules interact with one another.
 Repulsive forces between molecules assist expansion.
 Attractive forces assist compression.

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Molecular Interaction
• Repulsive forces:
assist expansion of gas
- significant when molecules are
close to one another
- operative at high pressures, when
intermolecular distances are near a
single molecular diameter
• Attractive forces:
assist compression of gas
- can have influence over a long
distance (close but not touching)
-operative at moderate pressures

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Compression Factors
• The compression factor of a gas can be
defined as
Z‘ = pVm
RT
where Vm is the molar volume, V/n
• Ideal gas: Z = 1
When Z ≠ 1 means that the gas is not
behaving as an ideal gas
• Intermediate Pressure: Z < 1
Compression is favoured, due to
dominance of attractive forces
• High Pressure: Z > 1
Expansion is favoured, as repulsive
forces come into play.
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Condensation
• CO2 gas compressed by a piston at 20oC:
A: P rises, in accordance with Boyle’s law
B: deviations from ideal gas behaviour
CDE: piston moves without any pressure
increase at all - non-ideal behaviour
• This line: vapour pressure (liq-gas)
• A liquid appears, just to the left of C,
amount of liquid increases moving from C
to D to E
• Pressure does not increase, since the gas is
beginning to condense
• E: sample is almost entirely liquid
Even a small volume reduction (E to F)
requires an immense increase in applied
pressure from the piston.
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Critical Constant
• The 31.04oC isotherm for CO2:
• If compression takes place at the so-called
critical temperature, Tc, the surface
separating the gas and liquid phases does
not appear, and horizontal parts of the
isotherm merge at the critical point - liquid
phase does not form above the critical
temperature.
• The critical temperature, molar volume and
pressure, Tc, Vc and pc, are called the critical
constants, which are unique to each
substance.
• Certain substances have a very dense phase
which can fill an entire volume at T > Tc, and
these are referred to as supercritical fluids.
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Johannes Diderik van der Waals (1837-1923), a Dutch

physicist, won the 1910 Nobel Prize in Physics for his work
on the equation of state for gases and liquids. This is an
semiempirical theory, which means it is based upon
experimental observations, combined with a rigorous
thermodynamic treatment.

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 nRT   an 2

P=  −  2 
 V − nb  V   n 2a 
 P + 2  (V − nb ) = nRT
 RT   a   V 
= − 2 
 Vm − b   Vm 
a = constant (the intermolecular forces between gas molecules,
unit, atm.L2mol-2)
b = constant (the volume of gas molecules, unit L.mol-1)
The a and b are known as Van der Waals coefficients 
specific for each gas.

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Justifying the Van der Waals Equation

The coefficients a and b are adjusted to model certain features of
the gas behavior & are dependent upon the attractive + repulsive
forces between molecules in the gas.
V – nb : nb is very small approximate volume occupied by the
molecules themselves.
Frequency & forces of the collisions are reduced by attractive
forces, by a strength proportional to n/V (molar concentration);
thus, pressure is reduced as the square of this concentration and is
written as: -a(n/V)2 (a = positive proportionality constant)
a and b should not be assigned specific molecular properties, but
rather, serve as coefficients which help to accurately model gas
behavior and can be assigned specifically to each type of gas.

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• The procedures that uses ‘light’ to measure chemical

concentration.
• Light is described as photon because of its ability to carry
energy.
• Spectroscopic analytical method are based on measuring
the amount of radiation produced or absorbed by
molecular or atomic species of interest.
• We can classify spectroscopic methods according to the
region of the electromagnetic spectrum involved in the
measurement.
• The regions in the spectrum include such as X-ray, Ultra
violet, Visible, Infrared(IR) and etc.
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The Electromagnetic Spectrum

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In spectrometric methods, the sample solution absorbs

electromagnetic radiation from an appropriate source and
the amount absorbed is related to the concentration of the
analyte in the solution.

Concentration of a solution is directly proportional to

the absorbance value of the solution.

A = absorbance,
ε = molar absorptivity (L mol-1cm-1), a = absorptivity (Lg-1cm-1)
b = optical pathlength (cm)
c = concentration (mol L-1).

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