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Chemical Thermodynamics
Molecular Scale
Macroscopic Scale
Sep-18 Chapter-1 2
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
Why Is It Useful?
Surroundings Closed E 0 , m 0
boundary
Open E 0 , m 0
Permeable/semipermeable
System
Rigid or Flexible
V 0 or V 0
Adiabatic
Simple systems: isotropic and Esimple w q0
homogeneous, electrically uncharged, closed system
No previous History
System
Subtleties of Equilibrium
• There exist materials (e.g., glass and steel) whose properties depend
on their manufacturing procedure, not only on the actual values of the
thermodynamic variables. Failure of the Thermodynamic description
can be used a posteriori to detect frozen nonequilibrium states.
• Thermodynamic systems can be in a less stable or more stable
equilibrium state. Solids and mixtures of chemical reactants are often
stuck in metastable states. Thermodynamic description of
metastable equilibria is normally valid.
T1 P1
V1 m1
… T1 P1
V1 m1
… T2 P2
V2 m2
t=0 t=t1
t=∞
Metastable equilibrium state
Sep-18 Chapter-1 6
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
Subtleties of Equilibrium
• For non-equilibrium systems (e.g., chemical reactors), the hypothesis
of local equilibrium is generally valid.
N 1
106
N N 1) A given dV (1 (mm)3) contains a big
number of molecules (>1010). The
T r Gas time interval between two successive
collisions between molecules is
1 m m 1015 L
3
around 10−12 s at normal P and T.
perturbation time t: is a
Validity of the t
local equilibrium De << 1 macroscopic time related
t to the duration of an
hypothesis Deborah Number
Sep-18
experiment (e.g. 1 s)
Chapter-1 7
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
Equations of state f P, , X 0
For a pure fluid: you set 2
intensive variables, you get
absolute control!
Sep-18 Chapter-1 8
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
SI Unit N
Pressure: is defined as the (Pascal)
Pa 2
applied force per unit of area m
Other P units
F
F 105 Pa 101325 Pa
Pressure P 1bar 1 atm
A A 760 mm Hg
1 atm
As we are still experiencing a transition period between the widespread
use of atm and mmHg on one hand and the use of SI units, bar and Pa,
on the other hand, students must be proficient in both sets of units.
Sep-18 Chapter-1 9
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
P down
to 10-11 mmHg
Capacitance manometer: As the gas Ionization Gauge: Electrons emitted from the hot
molecules strike the diaphragm, the force of filament collide with gas molecules and knock an
the collisions determines the space between electron free. The resulting cations are collected at
the diaphragm and the fixed electrode the center of the gauge, and the current they
assemblies. produce is a measure of the gas pressure.
Sep-18 Chapter-1 10
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
2
nN A m v 2U
P Collisional
V 3 3V P
nRT volume
Ideal V
monoatomic
M v2 3
gas
Um RT
Avx t
nN A 1
2 2 N coll
Sep-18 Chapter-1 V 2 11
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
Sep-18 Chapter-1 2 RT 12
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
3
The Maxwell- M 2
Mv 2
f v 4
2
ve
2 RT
Boltzmann distribution
2 RT
describes the influence
of M and T on
molecular speeds and
allows the calculation
of average properties.
8RT 2 RT
v v f v dv vmp
0 M M
3RT
v f v dv
2 2 Most experimental observations (like T itself)
v
0 M depend upon averages of molecular speeds
Sep-18 Chapter-1 13
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
Sep-18 Chapter-1 14
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
P1 1 P2 2 P3 3 P1 1 P3 3
f12 P1 , 1 , P2 , 2 0 f 23 P2 , 2 , P3 , 3 0
(b) f13 P1 , 1 , P3 , 3 0
(a) P2 w12 P1 , 1 , 2 w23 2 , P3 , 3
w1 P1 , 1 w2 P2 , 2 w3 P3 , 3
Reference Operational
thermometer Thermometer Sample
Thermocouple
Acoustic gas
thermometer
T 106 K
Sep-18 Chapter-1 16
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
P=1 bar
H 2O
Thermometric relationship Boiling
a bL point
L
Fixed T points H 2O
freezing
For calibration & point
parameterization purposes
Fahrenheit Centigrade
38.8 oC < Hg(l) < 356.7 oC
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
1.5
Ideal Gas P
thermometric
P a b 1.0
V=0.3 L
relationship
in the centigrade scale
V=0.6 L
100 P P0
0.5
P lim
0.0 P0 0 P100 P0
-300 -200 -100 0 100 200 300
Size of degree
T K o C Kelvin-Celsius relationship
Conventions
Water
in Kelvin and
Celsius scales
P
T T3
triple point T / K / C 273.15
o
(0.01 ºC)
P3 Water freezing point
273.16 K
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
ideal gas regime ↔ P < 0.1-10 bar and T > 273 K and M < 50 g/mol.
Large speed and long mean free path~70Å
Real (non-ideal) gas regime ↔ P > 0.1-10 atm or T < 273 K or M > 50 g/mol;
Low speed and/or short mean free path~1-5Å
P↑
…then intermolecular interactions DO count
and influence gas properties. Condensation of
real gases into liquids can be achieved either T↓
by gas compression and/or gas cooling.
Sep-18 Chapter-1 23
Phys. Chem. I
Chemical Thermodynamics
Chapter 1: Fundamental Concepts of Thermodynamics
n2 a
attractive
P 2 V nb nRT
V