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- solid
Microscopic Macroscopic
Statistical Mechanics
Quantum Chemistry
Properties: Properties:
Molecular masses Entropy
Molecular geometries Internal energy
Intermolecular forces Heat capacity
Chemical reaction rate
State of Matters
Physical
appearance State
specific density
Substances Liquid
variable shape
Gas
variable density
Multiple Phases
Single Phase
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)
CLB 10703 Sept 2016
CHAPTER 1
Pressure (P):
Temperature (T)
is the measurement of HEAT
is a form of energy can be quoted
in Joules (J) or Calories.
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
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
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
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
3
Higher
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…..
CLB 10703 Sept 2016
CHAPTER 1
Energy
Contributions to Energy
Phase of
Matter
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.)
CLB 10703 Sept 2016
CHAPTER 1
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.
Pressure
Measuring Pressure
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.
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.
Boyle’s Law
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
Charles Law
Gay-Lussac experiment
V = a + b ×T
dV
V=
V0 + ( ) × T
dT
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
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
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
CLB 10703 Sept 2016
CHAPTER 1
John Dalton
PT = PA + PB + PC + ..........
where PA, PB and PC = partial pressure of gas A, B and C
PT = total presure of the mixture
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
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.
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
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.
CLB 10703 Sept 2016
CHAPTER 1
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.
CLB 10703 Sept 2016
CHAPTER 1
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.
CLB 10703 Sept 2016
CHAPTER 1
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.
A = absorbance,
ε = molar absorptivity (L mol-1cm-1), a = absorptivity (Lg-1cm-1)
b = optical pathlength (cm)
c = concentration (mol L-1).