SKF3013 Physical Chemistry I

PROF. DR. RAMLI IBRAHIM

DR. NORLAILI ABU BAKAR
TERMINOLOGY

 System: region of chemical interest, e.g. reaction vessel,

characterized by properties such as Temperature (T), Pressure (P),
Volume (V).

 Surroundings: region outside the system and separated from the

system by a boundary.
boundary boundary

system system surroundings

surroundings
(b)
(a)
 Boundary

 Heat may be transferred between system and surroundings, and

the surroundings may do work on the system or vice versa. 2
System

 Open system: both energy and matter can be exchanged between the
system and its surroundings. E.g. Cup of tea

 Closed system: only energy can be transferred, either as work, or by

heat transfer. E.g. Cup of tea covered with plate.

BOUNDRY
BOUNDRY

Matter Work
Energy Heat
SYSTEM SYSTEM
SURROUNDINGS
SURROUNDINGS

Open System Closed System

Topic 1: First Law of Thermodynamic 3

System

 Isolated system: neither energy nor matter can be

exchanged. E.g. thermos
BOUNDRY

SYSTEM

SURROUNDINGS

Isolated System

4
Boundary

 Adiabatic : the system is thermally isolated, and so heat

transfer cannot occur, although work can be performed
on or by the system. BOUNDRY

Work
SYSTEM

SURROUNDINGS

Adiabatic Boundary

 Diathermic system: a system for which heat transfer is

possible.

Topic 1: First Law of Thermodynamic 5

Equilibrium
 properties always constant

Matters
  solid
 Liquid
 Gas

Laws in thermodynamics

 Zeroth’s
 First
 Second
 Third

Topic 1: First Law of Thermodynamic 6

THERMODYNAMIC FOR GAS SYSTEM

 Ideal gas obeys PV = nRT equation

where ; pressure (P), volume (V), (n) mol, (T) temperature and
gas constant (R) = 8.314 J K-1 mol-1
= 0.082 L atm K-1 mol-1
= 0.083 L bar K-1 mol-1
= 1.98722 cal K-1 mol-1
Note: 1 cal = 4.184 J
 
 Gases do not obey PV  nRT equation is called real gas
  Example: Real gas equations such as – van der Waals
   an 2 
 P  2 V  nb   nRT
   V 

 
where (a) and (b) are constant
  Variables: n, P, V and T
 Closed system: n fixed
 Open systen: n varies
 
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Zeroth’s Law ofLAW
THE ZEROTH Thermodynamic
OF THERMODYNAMIC
 
 
 If the two closed systems with fixed volumes are brought together so that
they are in thermal contact, changes may take place in the properties of
both.
 When there is no further change, a state is reached, called the state of
thermal equilibrium.
 Example : If A is in thermal equilibrium with B, and B with C, then A is
also in thermal equilibrium with C.
 This is called as the zeroth law of thermodynamic.
 Application: thermometer. boundary

A B C

TA = T B = T C
8
Workdone

V1
Pext

PS

V2 dx
 Work (w) = Force (F) x Displacement (d x)

 Thus, work (w): dw = F . dx

 Since

Volume = Area (A) x Distance (dx)



9
Workdone

 Since Volume final (V2) < Volume initial (V1):

dw =  Pext . dV IUPAC

  Since P depends on T and V, therefore

dw = - Pext(T,V).dV definition

 Total workdone ∫dw =  ∫ Pext(T,V).dV

2
w    Pext (T , V ) dV
1

 w can only be calculated if P, V or T is fixed

 IUPAC : work (w) is positive (+ve) values when work is done on the system of
interest and w is negative (-ve) values when the system does work on the
surroundings.
10
Workdone

w(-ve)

system surroundings

w(+ve)

 Process at fixed P, V, or T:
P is fixed (constant) is called at isobaric
V is fixed (constant) is called at isochoric
T is fixed ( constant) is called at isothermal

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HEAT (q)

 Heat is a form of energy. It can be transformed across the boundary of a

system.
 Heat flow : the transfer of energy due the difference in temperature
between the system and surroundings
 Heat always flows from high to low temperature
 Heat directly propotional to kinetic energy

 If Tsystem < Tsurrounding, q is positive (+ve), and heat flows into the system,
raising its internal energy U.
 
 If Tsystem > Tsurrounding, q is negative (-ve), and heat flows out of the system,
lowering its internal energy U.
q(-ve)
system
q(+ve)

surroundings 12
INTERNAL ENERGY (U)

 Internal energy (U) of a system is the total energy it contains as a

result of its physical state; under specified condition of T, P, and V.

 U is contributed by:
1. Kinetic energy of the individual molecule as the result of
molecular motion
2. Potential energy as the result of the interaction among
molecules
3. Kinetic energy and potential energy of the nuclei and electrons
in each individual molecule
 
 U does not depend on how that state was reached; state function.

Topic 1: First Law of Thermodynamic 13

STATE and PATH FUNCTION

  Macroscopic state of a system at equilibrium can be specified through

experiment by the value of small number of macroscopic variables.
  Example: temperature, T; pressure, P and volume, V (referred to state
function or thermodynamic variables).
 If x is a state function, initially at State I and finally at State II. It is found
that, x always the same.
PI,VI,TI PIl,VIl,TIl
 
  I Il
 
x (a)
  I Il
x (d)
x (b)
d
c x (c)
x(a) = x(b) + x(c) + x(d)

For any cyclic process: x = 0

 [x(b) + x(c) + x(d) ] – [x(a)] = 0

xII I = - x I II
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MATHEMATICAL ASPECT:DIFFERENTIAL

There are 2 types of differential:

1. Exact differential
2. Inexact differential x2
Exact differential e.g. dx
 Implies that
x1  dx  x2  x1  x
 x is a state function. E.g. Internal energy, U
 Value depends only the initial and final state

Inexact differential e.g. dy

  dy  y
 Y is not a state function
 Value depends on the path dy 
 Only work done, w and heat, q
 Therefore w and q are not state function (path function)

Topic 1: First Law of Thermodynamic 15

FIRST LAW OF THERMODYNAMIC
The First Law is concerned with conservation of energy, and may be stated as:
 ‘The energy of an isolated system is constant’

 This mean that energy can be neither created nor destroyed, only transferred between systems,
or between system and its surrounding.

Since ∆U of a system can be changed a given amount by either heat or work. (Expressed in
Joules (J) unit). If both heat and work are added to a system;
dU = dq + dw

The equation can also be written as: ∆U = q + w

Where:

 dU  U 2  U1  U Path independent

Example:  dw  w  dq  q Path dependent

If ∆U is negative, the system loses energy in heat that is evolved and work that is done
by the system.(not focused to how much amount involved but how equation is obeyed).
 

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REVERSIBLE AND IRREVERSIBLE PROCESS

Irreversible process
 Irreversible process (natural change): System and surroundings cannot
both be restored to their initial conditions (Occur when systems not in
equilibrium changes toward equilibrium).  All real processes are
irreversible. But it is possible to approach reversibility closely in some real
processes.
 A gas having pressure Psystem may experience compression or expansion
against the external pressure Pext
 
wirreversible = –  Pext. dV

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Reversible process
 Reversible process: process that can be reversed at any point by making
an infinitesimal change.
  The process requires an absence of friction, a balancing of internal and
external pressures, and time to re establish equilibrium after each
infinitesimal step.
Assume : Pext = Psystem + dP
Equation : w = – Pext. dV becomes
w = – ( Psystem + dP )dV
= – Psystem dV – dP.dV

Since dP << ,  dP.dV  0

hence w = –  Psystem. dV Psystem = Ps

 This general equation and for simplicity, Ps  P

  
w   PdV

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WORK DONE FOR REVERSIBLE
PROCESS OF IDEAL GAS

a) Constant Pressure, P (Isobaric)

General equation: dw = –Pext dV
Reversible process: Pext = Psystem = P so dw = -PdV
V2
 
   
w   P dV  P dV   P (V2  V1 )
V1
 
w = – P.V
 
b) Constant Volume, V (Isochoric)
dw = - PdV
Since V = constant  dV = 0
 dw = - P (0) = 0
w = 0

Topic 1: First Law of Thermodynamic 19

c) Constant Temperature, T (Isothermal)

Reversible process: Pext = Psystem = P so dw = -PdV

Ideal gas : PV= nRT


w   PdV

nRT
Substitute: P 
V
dV
w  nRT
V

dV V P
w   nRT  V
  nRT ln 2   nRT ln 1
V1 P2

at this condition, w is wmax .Why?

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d) For two different temperature, T1 and T2

Ideal gas equation : PV = nRT

 
PdV = nRdT
 
Since dw = - PdV
 dw = -nRdT
w =  dw = – nR  dT

w = – nR (T2 – T1)
 

21
EXAMPLE 1
 One mole of an ideal gas expands from 5 bar to 1 bar at 298 K. Calculate w,
(a) for a reversible expansion and
(b) for an expansion against a constant external pressure of 1 bar.
 
 ANSWER 
 
     (a) dw = - PdV
  w   PdV 
  Subtitute P with P 
nRT
  V
dV
w  nRT
V
dV V P
w   nRT 
V
  nRT ln 2   nRT ln 1
V1 P2
P1
wreversible  nRT ln
P2
5
wreversible  (1 mol)(8.314 J K -1 mol-1 )(298K ) ln
1
wreversible  3988 J 22
  (b) 
 
 ANSWER (b)  dw = - Pext.dV
V2
 
w    Pext dV  Pext  dV   Pext (V2  V1 )
V1
wirreversible   Pext (V2  V1 )
 nRT nRT 
wirreversible   Pext   
P
 ext P1 

 Pext 
wirreversible  nRT 1  
 P1 

 1
wirreversible  (1 mol)(8.314 J K -1 mol-1 )(298K ) 1  
 5
wirreversible  1982 J
More work is done on the surroundings when the expansion
is carried out-reversibly
23
Example 2
(a) A cylinder fitted with a piston contains 5.00 L of a gas at a pressure of 4.00
atm. The entire apparatus is immersed in a water bath to maintain a constant
temperature of 25 0C. The piston is release and the gas expands until the
pressure inside the cylinder equals to the atmospheric outside, which is 1
atm. Assume ideal gas behavior and calculate the amount of work done by
the gas as it expands at constant temperature.
 
(b)The experiment described in part (a) is repeated, but this time a weight,
which exert a pressure of 2 atm, is placed on the piston. When the gas
expands, its pressure drops to this 2 atm pressure. Then the weight is
removed and the gas is allowed to expand again to a final pressure of 1 atm.
Through out both expansions the temperature of the apparatus was held at a
constant temperature, 25 0C. Calculate the amount of work performed by the
gas in each steps. How does the combined total amount of work in this two
step expansion compare to the amount of work done by the gas in the one
step expansion described in part (a).

Topic 1: First Law of Thermodynamic 24