Physical Chemistry

Dae Yong JEONG

Inha University

1.1 STATE OF A SYSTEM

Boundary

Universe

Insulation or heat conduction

Or semipermeable (matter transfer)

system
Surrounding

Definitions

System: the object of interest

Surrounding: rest of the space which gives an effect on system
Boundary: The surface dividing the TD system from the
surroundings

System
matter
energy

energy

matter

matter

energy

energy

energy

surrounding

surrounding

surrounding

Open system

Closed system

Isolated system

Depending on the property of the boundary,

the TD system can be classified into;

matter

Open system: mass and energy can transfer bw

System & Surrounding
Closed system: energy can be transfer bw
System & Surrounding, but NOT mass
Isolated system: neither mass nor energy can
transfer bw system & surrounding

Homogeneous: its properties are uniform throughout

For example: single phase
Heterogeneous: contains more than one phase:
For example: water + ice at 0 oC

Physical state ()

Two meanings of State

State of matter ( )

Gas
Liquid
Solid
Plasma

Physical state: P, V, T, n ( )

How to describe the TD system macroscopically?

How to describe the energy state (change) in TD system?

What kind of variables can be used to describe the TD system?

A few macroscopic properties: T, P, V, n, m

As possible as, simple and small # of variables.

Can give an information on energy and physical state!!

Follow all of the rules of calculus

,
.

The state of a system at Equilibrium;

Can be described by state variables (ex, T, P, V, n1..) being

independent of the history of the system.

State of a system = f (state variable) : state function

state variables , system

.
state ,
.

Classification of TD Variables

Extensive variables: (ex) V, mass, S, n1

Only have values for a system as a whole

Intensive variables: (ex) P, T, density

Independent of the size of the system.

They can be either intensities or densities.

Densities: obtained from dividing a extensive variable

by another extensive variable (ex. Per mole, per unit
volume)

Intensive state of the system; described by intensive

variables
Extensive state of the system: described by intensive
variable and at least one extensive variable.

Equilibrium state in TD

Equilibrium state: Properties independent of time and having no fluxes

(e.g., no heat flowing through the system)
TD system in Eq. can be specified by a small number of state
variables.

No history information!!

For examples,

For ideal gas: PV = nRT

Multi-components system: the information on composition should be given.

If a liquid system is in the form of small droplets, the surface area has to be
given.
If a system is in an electric or magnetic field, this may have an effect on its
properties, and then electric field strength and magnetic field strength become
state variables.
In general, gravitational field is ignored.

Change of state

It is difficult to know the absolute value of energy.

We could just know the energy change (E) involved in the
change of state.
To know the change, we could be able to define the initial and
final states.
However, the change is sometimes dependent on the path which
is determined by the process.

Path: sequence of intermediate states

P (bar)

Process: describe the path

Reversible: always in eq.
Irreversible: defines direction of time
Adiabatic: no heat transfer bw system and surrounding
Isobaric: constant pressure
Isothermal: constant temp.
Constant volume

If we could define the initial and final state and know the process,
then energy change can be known.
( , , ,
.)

final
state
Initial
state

T (K)

Reversible & Irreversible process

Reversible process

A process that takes place through a series of eq. states

However, an infinitesimal change in the external conditions will cause a change in the
direction of process. ( .)

Irreversible process: the direction of a process cannot be changed by an

infinitesimal change in external conditions

Although actual processes in nature are never reversible, the consideration of reversible
processes permit changes in the state functions to be calculated.

Since changes in state functions depends only on the initial & final states, we
can imagine for computational purposes that a reversible process connects
these two states.

1.2 The 0th Law of TDs

0th law

(A & C: thermal eq.) and (B & C: thermal eq.)

A & B: thermal eq.
Give the definition of Temp.

At thermal eq., T is the same.

Measure the temp. (experimental) Temp. is same.
Two state are in thermal eq.
No thermal change temp. is same.

Why temp.?
Temp. gives on information on thermal
energy.

Lets consider the fluid first.

Fluid: either a gas or a compressible liquid.

Why fluid first? From our experiences,

At const. P V changes
At const. V P changes
P and V are independent variables.
Quite simple to specify the physical state with P and V
for a given composition!!

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Boyles law

For gas state,

Thermal energy (T) vs physical state (P, V)

PV=constant at a specific T

P2V2 T2
PV
PV

or 2 2 1 1
P1V1
T1
T2
T1
PV

nR : The ideal gas equation of state

T
R : gas constant

n : the amount of gas

11

1.3 The ideal gas temp. scale

Lets define the temp. with variables for physical state

PV
PV

T lim
lim

P 0 nR
P 0

The unit of TD temp, Kelvin or 1K is defined as the fraction 1/273.16 of the

temperature of the triple point of water.
0 K: absolute zero

t / o C T / K 273.05

Pressure (P) = Force/Unit area

SI unit: Pascal, Pa = 1N/m2

1 bar = 105 Pa
1 atm = 101325 Pa = 1.01325 bar

mole (n) is the number of 12C atom for 0.012 kg.

1 mole 6.02214 x 1023 #/mole : Avogadro number (NA)

Number of molecules = n x NA
Molar mass (M) = NA m (kg/mol)

m: the mass of a single molecule

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Gas constant (R)

R = 8.31451 J/(K-mol)
R = kB x NA
= (Boltzmann constant = 1.3802 x 10-23 J/K) x (Abogadro Number = 6.02214 x 1023 #/mole)
Here, 1 J = 1 Pa x m3 (energy) = (Pressure x volume)

Volume (V)

For an ideal gas, at 0 oC (273.15 K) and 1 atm 1 mole of ideal gas has 22.414 liters

P0V0
const R
T0

Example 1.2

Temperature

14

Pressure

Microscopic: container
15

1.4 Ideal gas mixtures and Daltons law

Mixture of ideal gas

n = n1 + n2 + n3 + .

P (n1 n2 ) RT / V P1 P2

P
i

Pressure (microscopically)
Atom (molecule) hits the wall of vessel. pressure
# of atoms (for the same temp. and volume) high pressure
Temp. increases pressure increases.
16

1.5. Real Gases and the Virial Equation

What is ideal gas?

What are the properties of real gas?

. (Liquid/solid: .)
Real gases behave like ideal gas in the limits of low pressures and high temp., but
they deviate significantly at high P and low T.

How to modify the ideal gass equation for the real gas?

Virial (force) Equation

Compressibility factor

PV
B C
1 2 ...
RT
V V

B: 2nd virial coefficient

B = 0 at Boyle Temp. (TB)
B changes with temp.

Low P Z < 1
( )
High P Z > 1 (

)

At Low T
Z (
)
At High P

(),
Z>1

17

In fact, it is more convenient to use P as the experimental

variable than V.

PV
1 B ' P C ' P 2 ...
RT

PV
B C
1 2 ...
RT
V V

RT BRT CRT
2 3 ...
V
V
V

RT BRT
P

2
V V
2

RT
Z 1 B
V
'

' BRT
2

2 2

' R T
C 2 ...

B B ' RT
C B ' BRT C ' R 2T 2

18

CRT
3
V

RT
2
V

BRT
2
V

..

1.6 P-V-T surface for a 1-component system

Triple point
The state where Gas-liquid-solid co-exist
19

1.7 critical phenomena

For a pure substance, there is a critical point (Pc, Tc)

End point for Liquid-Gas coexistence (Fig. 1.12)

Tc: highest temp. at which condensation of a gas is possible
Pc: highest pressure at which a liquid will boil when heated.

2P
P
0 and 2
0

At Tc,

T TC

T TC

Tc : Isothermal compressibility

1 V

V P T

( (steam)
)

20

3 step process to liquefy gas

without phase transition

Pressure

Solid

ve
cur

Expansion
at const. T

L-V
apo
r co
exi
ste
nce

S-L coe
xistenc
e

curve

cooling
at const. P
Critical
point

Liquid

compression
at const. T

Vapor

Triple point
S-Vapor
coexistence curve

Sublimation temp.
Freezing temp.
Boiling temp.

Temperature

(TC) (PC) :
21

Critical Point

22

1.8 The Van Der Waals Equation

Real gas

Real gas is not a point particle but has a certain volume. So, the (empty) volume in ideal gas Eq.
should be replaced.

P(V b) RT

b: the volume of one mole of real gas

Always, Compressibility > 1

Attraction force bw gases (Van der Waal force!!)

How to modify the ideal gas Eq.? Which variable should be modified?

P P

a
V

.( )

23

1.8 The Van Der Waals Equation

van der Waals Equation P

Molar volume is large, b is negligible ideal gas behavior

Useful for gas-liquid phase separation

(Math)
Compressibility factor for van der Waals gas
Z

a
(V b) RT
2
V

PV
V
a
1

RT V b RT V 1 b

for b

a
RT V

Analysis
At low temp. a is relatively more
important (~ force bw gases)
At high temp. b is relatively more
important (~ gas volume)

a 1 b

Z 1 b
...
RT

V V
1
a
Z 1
b
P ...
RT
RT

Calculate the van der Waals constant from the critical constants for a
gas
24

Van der Waals constant

25

1.9 Description of the state of a system w/o

chemical reactions

Number of degree of freedom (F)

# of independent variables required

Independent Intensive variable, F = Ns + 1

Ex: one component F = 2
Gas A T1, P1
.

P2
S

Ns: # of species

P3

For two-phase w/o chemical rxn

For one-phase system w/o chemical rnx,

Ex: one component F = 1

Liquid-solid , T2
P2

P1

For three-phase w/o chemical rxn

Ex: one component F = 0

G-L-S T3, P3 .

T1
T2

T3

Ns+2 variables are required to describe

the extensive state of a homogeneous
one-phase system.
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1.10 Partial molar properties

For the mixtures of gases and mixtures of liquids

V V 1n1 V 2 n2 ... V n nn

Partial molar volume:

V V 1 x1 V 2 x2 ... V n xn
V

V i
ni T , P ,{n ji }

V i dni : The change in V when an infinitesimal

amount (dni) of this substance is added to the
solution at constant T, P, and all other nj.

dV V 1dn1 V 2 dn2 V 3dn3 .... V n dnn

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Next class

First Law of Thermodynamics

28

? , ?

Is it possible to design a ship that is purely powered by the

heat of the ocean?

Take water from the ocean, absorb the heat from water and turn
water into ice, then drop the ice balls behind?

,
?

?
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Q: Real Gases and the Virial Equation

Virial Equation Z PV 1 B C2 ...

RT

Q: 200 oC (isopropanol) .
B = - 388 cm3/mol
C = -26,000 cm6/mol2
200 oC, 10 bar V Z .
(1)
(2)

A)

RT 83.14473.15

3,934 cm 3 / mol, Z 1
P
10

PV
B C
1 2
RT
V V

V = 3,488 cm3/mol
Z = 0.8866
13% .

, 200 oC, 10 bar

.
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