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CHAPTER 1 CHAPTER 1

Introduction to Physical Chemistry

Topics :
1. Overview of Physical Chemistry
2. Matter and Energy Math Chemical Law of
3. The Properties of Gas methods Systems physics
4. The Gas Laws Reasoning chemical phenomena
5. Spectroscopy Techniques Predicting properties + reactions

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Chemical System Study Physical Chemisty Fields

chemical Aggregation of - gas a) Quantum Chemistry
bonding atoms/molecules application of quantum mechanics to atomic structure &
atoms molecules Bulk - liquid
molecular bonding.
- solid b) Statistical Mechanics
Microscopic Macroscopic deduce the macroscopic properties of matter from the
Statistical Mechanics properties of molecules in a system.
c) Thermodynamics
Quantum Chemistry study of heat, work, energy and the changes they produce in
Properties: Properties: the states of systems.
Molecular masses Entropy
Molecular geometries
d) Kinetics
Internal energy
Intermolecular forces Heat capacity study of rate processes such as chemical reactions, diffusion
Chemical reaction rate and the flow of change in electrochemical cell.

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State of Matters
Physical Multiple Phases
appearance State

specific shape Pure component Heterogeneous

Solid one - multiphase mixtures multiple
specific density component Pure component Homogenous component
Liquid - 1 phase mixtures
Substances
variable shape
Gas
Single Phase
variable density

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Changing of State Pressure (P):

Atmospheric Pressure is measured by the

Solid level of Hg (mm or cm) in the glass tube.
ts, P = 1 atm tf, P = 1 atm
Without air, the level of Hg in the glass
Gas Liquid tube is equal to the level of Hg in the
tb, P = 1 atm tray at sea level.
The level of Hg is 760 mm or 76 cm at
tf = freezing/melting temperature
tb = boiling/condensing temperature sea level, so atmospheric pressure is
ts = sublimation temperature 760 mm Hg (torr) = 1 atm = 1.013 bar
= 101.325 kPa 760 mm
temperature (t)
& are states variables or properties
pressure (P)
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Temperature (T)
Quantifying Matter
Substance: A pure form of matter
is the measurement of HEAT Amount of substance: Reported in terms of moles.
1 mol of a substance contains as many entities as exactly 12 g of
is a form of energy can be quoted
carbon-12 (ca. 6.02 x 1023 atoms)
in Joules (J) or Calories.
Avogadros Number: NA = 6.02 x 1023 mol-1
Extensive Property: Dependent upon the amount of matter in
Unit of temperature = C (Celsius), K (Kelvin) the substance (e.g., mass & volume)
Intensive Property: Independent of the amount of matter in a
T (K) = T (C) + 273.15
substance (e.g., mass density, pressure and temperature)
Kelvin also called thermodynamic temperature
Molar Property: Xm, an extensive property divided by the
0 K = absolute temperature
amount of substance, n: Xm = X/n
Molar Concentration: Molarity= moles of solute dissolved in
liters of solvent: 1.0 M = 1.0 mol L-1

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SI vs. Gaussian Units SI Derived Units

Derived quantity Name Symbol
Older literature sources and many Americans still use the volume cubic meter m3 or L or dm3
Gaussian system of units, so it is useful to understand the speed, velocity meter per second m/s
relationship between the SI and Gaussian systems. acceleration m. per s. squared m/s2 or m s-2
wave number reciprocal meter m-1
SI Units Gaussian Units mass density kg per cubic m kg/m3 or kg m-3
Name Symbol Name Symbol Conversion frequency hertz Hz : s-1
meter m centimeter cm 0.01 m force newton N : kgms- 2
kilogram kg gram g 0.001 kg pressure, stress pascal Pa : N/m2 : kgm-1s-2
second s second s energy, work, heat joule J : Nm : kgm2s-2
power, radiant flux watt W : J/s : kgm2s-3
ampere A biot Bi 10 A electric charge coulomb C : As
kelvin K kelvin K electric potential voltan V : W/A : kgm2s-3A-1
mole mol Mole mol magnetic field tesla T : A/m
candela cd Stilb sb 104 cd m-2
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SI vs. Gaussian Derived Units Example :

Many important units, some with special names and symbols,
N
can be derived from the SI base units: L atm 10 3 m 3 101.3 10 3
Derived quantity Symbol Conversion m2
erg (energy) erg 1 erg = 10-7 J 101.3 N m
dyne (force) dyn 1 dyn = 10-5 N
gauss (magnetic field) G, Gs 1 G = 10-4 T 101.3 J
Other units
calorie (energy, thermo) cal 1 cal = 4.184 J
g mol g mol L mL g
calorie (food energy) Cal 1 Cal = 1 kcal = 4184 J 103
electron volt (energy)* eV 1 eV = 1.602 177 33 x 10-19J mol L mol L 103 mL cm3 cm3
micron (distance) 1 = 10-6 m = 1 m
Angstrom (distance) 1 = 10-10 m

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Atmospheric pressure is the pressure causes

Pressure (P) by mass of air exerting on ground.
force that exerts on unit area
1
Lower
F force
P 2
A area Density of air

Unit of Pressure : 3
Higher
N Pound
Pascal , psi Gravitational force at higher altitude is less dense than at
m2 in2 lower altitude.
P@ 1 < P@ 2 < P@3
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Other Properties
Energy
- 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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CHAPTER 1 CHAPTER 1

Contributions to Energy The Properties of Gases

a) The Perfect Gas
States of gases
Gas laws
Kinetic model of gases
b) Real Gases
Molecular interactions
Van der Waals equation
Principle of corresponding states

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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.
Phase of A perfect gas is pictured as a collection of molecules or atoms
which undergo continuous random motion (or Brownian
Matter 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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State of Gases Pressure

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Pressure Exerted by Gases Measuring Pressure

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Temperature Thermal Equilibrium

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.
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 The Gas Laws

Individual Gases :
Boyles Law
Charles Law
Avogadros Law
Perfect (Ideal) Gas Equation
Mixtures of Gases :
Daltons Law
Mole Fractions

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CHAPTER 1 CHAPTER 1

Boyles Law Boyles Law

Boyles Law states that the volume of a fixed mass of
gas is inversely proportional to its pressure at constant
temperature.
1 1
V or P
P V
P V constant

P1 V1 P2 V2

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Rationalizing Boyles Law Charles (Gay-Lussacs) Law

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Charles Law Effects of Changing Temperature

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 V2

T1 T2

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CHAPTER 1 CHAPTER 1

Rationalizing of Charles Law Avogadros Law

Avogadros 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 The Gas Constant

Boyle' s Law : PV constant
V
Charles' Law : constant
T
n
Avogadro's Law : constant
V
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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For a fixed number of moles of gas (n = constant): John Dalton

PV P1V1 P2V2 Combination of Boyles
constant or & Charles Laws
T T1 T2
At S.T.P. : 1 mol of any gas occupies 22.4 dm3 at 273.15 K (0oC)
and 101325 Pa (1 atm).
Molar volume of gas, Vm = 22.4 dm3 mol-1 ( or 22.4 L mol-1)

While at S.A.T.P. : 1 mol of any gas occupies 24.79 dm3 at

298.15 K (25oC) and 101325 Pa (1 atm).
Molar volume of gas, Vm = 24.79 dm3 mol-1 ( or 24.79 L mol-1)

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CHAPTER 1 CHAPTER 1

Daltons Law of Partial Pressure Mole Fraction

State that in a mixture of gases that do not interact with one
PA = A x P T
another, the total pressure of the mixture is the sum of the
partial pressure of the constituent gases. where A = mole fraction of gas A in the mixture

PT PA PB PC ..........
nA
where PA, PB and PC partial pressure of gas A, B and C A =
nT
PT total presure of the mixture n A = no. of moles of gas A in the mixture
n T = total no. of moles in the mixture

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Real Gases Molecular Interaction

Real gases do not obey the perfect gas law exactly. Deviations Repulsive forces:
from the law are particularly important at high pressures and assist expansion of gas
low temperatures, especially when a gas is on the point of - significant when molecules are
condensing to liquid. close to one another
- operative at high pressures, when
Molecular Interactions intermolecular distances are near a
Real gases show deviations from the perfect gas law single molecular diameter
because molecules interact with one another. Attractive forces:
Repulsive forces between molecules assist expansion. assist compression of gas
Attractive forces assist compression. - can have influence over a long
distance (close but not touching)
-operative at moderate pressures

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Compression Factors Condensation

The compression factor of a gas can be CO2 gas compressed by a piston at 20oC:
defined as A: P rises, in accordance with Boyles law
B: deviations from ideal gas behaviour
Z = pVm
CDE: piston moves without any pressure
RT increase at all - non-ideal behaviour
where Vm is the molar volume, V/n This line: vapour pressure (liq-gas)
Ideal gas: Z = 1 A liquid appears, just to the left of C,
When Z 1 means that the gas is not amount of liquid increases moving from C
behaving as an ideal gas to D to E
Intermediate Pressure: Z < 1 Pressure does not increase, since the gas is
Compression is favoured, due to beginning to condense
dominance of attractive forces E: sample is almost entirely liquid
High Pressure: Z > 1 Even a small volume reduction (E to F)
Expansion is favoured, as repulsive requires an immense increase in applied
pressure from the piston.
forces come into play.
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Critical Constant
The 31.04oC isotherm for CO2:
If compression takes place at the so-called
Van der Waals Equation
critical temperature, Tc, the surface Johannes Diderik van der Waals (1837-1923), a Dutch
separating the gas and liquid phases does
physicist, won the 1910 Nobel Prize in Physics for his work
not appear, and horizontal parts of the
on the equation of state for gases and liquids. This is an
isotherm merge at the critical point - liquid
phase does not form above the critical
semiempirical theory, which means it is based upon
temperature. experimental observations, combined with a rigourous
The critical temperature, molar volume and thermodynamic treatment.
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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Justifying the Van der Waals Equation

Van der Waals Equation
The coefficients a and b are adjusted to model certain features of
2 the gas behavior and are dependent upon the attractive and
nRT an repulsive forces between molecules in the gas.
P 2 n 2a
V nb V P 2 V nb nRT V nb : nb is very small approximate volume occupied by the
V molecules themselves.
RT a Frequency and forces of the collisions are reduced by attractive
2
Vm b Vm forces, by a strength proportional to n/V (molar concentration);
thus, pressure is reduced as the square of this concentration and
a = constant (the intermolecular forces between gas molecules) is written as:
b = constant (the volume of gas molecules) -a(n/V)2 : a is a positive proportionality constant
The a and b are known as Van der Waals coefficients a and b should not be assigned specific molecular properties, but
specific for each gas. 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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Spectroscopy Techniques Spectroscopy Techniques

The Electromagnetic Spectrum
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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Spectroscopy Techniques
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.

Beers Lambert Law

The concentration of a solution is directly proportional to the
absorbance value of the solution.
A=abc A=bc
A = absorbance,
= molar absorptivity (L mol-1cm -1), a = absorptivity (Lg-1cm -1)
b = optical pathlength (cm)
c = concentration (mol L-1).

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