PROF. DR.

RAMLI IBRAHIM
DR. NORLAILI ABU BAKAR


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

Heat may be transferred between system and surroundings, and
the surroundings may do work on the system or vice versa.




2
system
surroundings
boundary
system
surroundings
boundary
(a)
(b)
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.


Matter
Energy
SYSTEM
SURROUNDINGS
BOUNDRY
Open System
Work
Heat
SYSTEM
SURROUNDINGS
BOUNDRY
Closed System
Topic 1: First Law of Thermodynamic 3
System
SYSTEM
SURROUNDINGS
BOUNDRY
Isolated System
4
Isolated system: neither energy nor matter can be
exchanged. E.g. thermos
System
Adiabatic : the system is thermally isolated, and so heat
transfer cannot occur, although work can be performed
on or by the system.






Diathermic system: a system for which heat transfer is
possible.



Topic 1: First Law of Thermodynamic 5
Work
SYSTEM
SURROUNDINGS
BOUNDRY
Adiabatic Boundary
Equilibrium
properties always constant

Matters
solid
Liquid
Gas

Laws in thermodynamics

Zeroths
First
Second
Third


Topic 1: First Law of Thermodynamic 6
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



where (a) and (b) are constant
Variables: n, P, V and T
Closed system: n fixed
Open systen: n varies


7
( ) nRT nb V
V
an
P =
|
|
.
|

\
|
+
2
2


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.
8
A
T
A
= T
B
= T
C

boundary
B C
Zeroths Law of Thermodynamic
Volume = Area (A) x Distance (dx)





Work (w) = Force (F) x Displacement (d x)

Thus, work (w): dw = F . dx

Since







9
P
ext

P
S

V
1

V
2

dx
Since Volume final (V
2
) < Volume initial (V
1
):

dw = P
ext
. dV IUPAC

Since P depends on T and V, therefore

dw = - P
ext
(T,V).dV definition

Total workdone dw = P
ext
(T,V).dV



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
}
=
2
1
) , ( dV V T P w
ext




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

11
system
surroundings
w(-ve)
w(+ve)
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 T
system
< T
surrounding
, q is positive (+ve), and heat flows into the system,
raising its internal energy U.

If T
system
> T
surrounding
, q is negative (-ve), and heat flows out of the system,
lowering its internal energy U.

12
system
surroundings
q(-ve)
q(+ve)
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
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, Ax always the same.





14
I
P
Il
,V
Il
,T
Il

P
I
,V
I
,T
I

Il
Ax (a)
I Il
Ax (c)
Ax (b)
Ax (d)
c
d
Ax(a) = Ax(b) + Ax(c) + Ax(d)
For any cyclic process: Ax = 0
[Ax(b) + Ax(c) + Ax(d) ] [Ax(a)] = 0
Ax
II I
= - Ax
I II

There are 2 types of differential:
1. Exact differential
2. Inexact differential

Exact differential e.g. dx
- Implies that
- x is a state function. E.g. Internal energy, U
- Value depends only the initial and final state

Inexact differential e.g. dy
- Y is not a state function
- Value depends on the path
- Only work done, w and heat, q
- Therefore w and q are not state function (path function)

Topic 1: First Law of Thermodynamic 15
x x x dx
x
x
A = =
}
1 2
2
1
}

= = y dy dy
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:




Example: 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).

16
U U U dU A = =
}
1 2
}
= q dq
}
= w dw
Path dependent
Path independent

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 P
system
may experience compression or expansion
against the external pressure P
ext

w
irreversible
= } P
ext
. dV

17
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 : P
ext
= P
system
+ dP
Equation : w = P
ext
. dV becomes
w = ( P
system
+ dP )dV
= P
system
dV dP.dV

Since dP << , dP.dV ~ 0

hence w = } P
system
. dV P
system
= P
s

This general equation and for simplicity, P
s
P


18
}
= PdV w
a) Constant Pressure, P (Isobaric)
General equation: dw = P
ext
dV
Reversible process: P
ext
= P
system
= P so dw = -PdV



w = P.AV

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
) (
1 2
2
1
V V P dV P dV P w
V
V
= = =
} }
c) Constant Temperature, T (Isothermal)

Reversible process: P
ext
= P
system
= P so dw = -PdV
Ideal gas : PV= nRT



Substitute:








at this condition, w is w
max
.Why?

20
V
nRT
P =
}
= PdV w
}
=
V
dV
nRT w
}
= = =
2
1
1
2
ln ln
P
P
nRT
V
V
nRT
V
dV
nRT w
d) For two different temperature, T
1
and T
2


Ideal gas equation : PV = nRT

PdV = nRdT

Since dw = - PdV
dw = -nRdT
w = } dw = nR } dT

w = nR (T
2
T
1
)


21
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.


22


J 3988
1
5
ln ) 298 )( mol K J mol)(8.314 1 (
ln
1 - 1 -
2
1
=
=
=
reversible
reversible
reversible
w
K w
P
P
nRT w
ANSWER
(a)



dw = - PdV
}
= PdV w
Subtitute P with
V
nRT
P =
}
=
V
dV
nRT w
}
= = =
2
1
1
2
ln ln
P
P
nRT
V
V
nRT
V
dV
nRT w
23
ANSWER (b)

(b)

J 1982
5
1
1 ) 298 )( mol K J mol)(8.314 1 (
1
) (
1 - 1 -
1
1
1 2
=
(

=
(

=
(

=
=
le irreversib
le irreversib
le irreversib
ext
ext le irreversib
ext le irreversib
w
K w
P
P
nRT w
P
nRT
P
nRT
P w
V V P w
ext
More work is done on the surroundings when the expansion
is carried out-reversibly
dw = - P
ext
.dV
) (
1 2
2
1
V V P dV P dV P w
ext
V
V
ext ext
= = =
} }
(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
0
C. 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
0
C. 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