04 First Law of Thermodynamics

2011 Imam Siswanto Kimia Fisika I
KIMIA FISIKA I
First Law of Thermodynamics
universitas airlangga
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2
This law is merely the law of conservation of energy, namely, that energy
can be neither created nor destroyed.

Matematically :

AE + w = q
or
AE = q - w

Since internal energy depends only on the state of the system, then the
change in the energy , involved in going from a state where the energy is
E
1
to another state where the energy is E
2
must be given by
AE = E
2
E
1

3
}
= A
2
1
V
V
pdV q E
Under special conditions these equation may take on special forms as follows :
1. Constant volume, dV = 0, dw = 0 and AE = q
2. Opposing pressure zero, p = 0, dw = 0 AE = q
3. Opposing pressure constant, w = p(V
2
V
1
) and AE = q p(V
2
V
1
)
4. Opposing pressure variable, p must be known as a function of V for the given
situation.
It must be clearly understood that, except under the condition to be pointed out
below, the pressure which determines the amount of work done is not the
pressure of the gas P, but the pressure against which the gas is working, namely,
p.
4
Reversibility and Maximum Work
The maximum work is obtainable from a system when any change taking
place in it is entirely reversible.

Example :
1. Find the work done when 2 moles of hydrogen expand isothermally from
15 to 25 liters against a constant pressure of 1 atm at 25
0
C.

2. Calculate the work performed when 2 moles of hydrogen expand
isothermally and reversibly at 25
0
C from 15 to 25 liters.
5
The Enthalpy af a System
Thermal changes at constant pressure are most conveniently expressed in
terms of another function, H, called the enthalpy o the relationr heat content
of a system.

This function is defined by the relation :

H = E + PV

When the pressure remains constant throughout the process, then

AH = AE + PAV

6
Heat Capacity
The amount of heat required to raise the temperature of the system 1 degree
is

and C is thus the heat capacity of the system.

While dq = de + pdv, therefore

When the volume is held constant

It tell us that C
v
is the rate of the change of the internal energy with
temperature at constant volume.

dq
C
dT
=
dE pdv
C
dT
+
=
v
v
E
C
T
c
| |
=
|
c
\ .
7
Heat Capacity
However, when the heat absorption occurs reversibly at constant pressure, when
p = P and

But, if H = E + PV is differentiated with respect to T at constant P we get

Consequently,

It tell us that C
p
is the rate of the change of the internal energy with temperature
at constant pressure.

p
P P
E V
C P
T T
c c
| | | |
= +
| |
c c
\ . \ .
P P P
H E V
P
T T T
c c c
| | | | | |
= +
| | |
c c c
\ . \ . \ .
p
P
H
C
T
c
| |
=
|
c
\ .
8
Heat Capacity
From the previous definition of C
v
and C
p
we have

But H = E + PV. Differentiating this equation with respect to temperature at
constant pressure we obtain

Then
The difference between the two heat capacities
p v
P v
H E
C C
T T
c c
| | | |
=
| |
c c
\ . \ .
P P P
H E V
P
T T T
c c c
| | | | | |
= +
| | |
c c c
\ . \ . \ .
p v
P P v
E V E
C C P
T T T
c c c
| | | | | |
= +
| | |
c c c
\ . \ . \ .
9
Heat Capacity
The internal energy, E, in general, will be a function of any two of three
variables (P, V, T). If we take T and V as our independent variables, then

E = f(V,T)
And

Dividing both sides of the equation by dT and imposing the condition of
constant pressure, we get

V T
E E
dE dT dV
T V
c c
| | | |
= +
| |
c c
\ . \ .
P V T P
E E E V
T T V T
c c c c
| | | | | | | |
= +
| | | |
c c c c
\ . \ . \ . \ .
10
Heat Capacity
Finally,

p v
V T P P v
E E V V E
C C P
T V T T T
c c c c c
| | | | | | | | | |
= + +
| | | | |
c c c c c
\ . \ . \ . \ . \ .
T P P
E V V
P
V T T
c c c
| | | | | |
= +
| | |
c c c
\ . \ . \ .
Perfectly general equation
11
Dependence of State Function on Variables
If we start with the fact that E = f(T,V), then

According to the second law of thermodynamics :

Then

V T
E E
dE dT dV
T V
c c
| | | |
= +
| |
c c
\ . \ .
T V
E P
T P
V T
c c
| | | |
=
| |
c c
\ . \ .
v
V
P
dE C dT T P dV
T
( c
| |
= +
| (
c
\ .

12
Similar consideration of H as a function of T and P gives

According to the second law of thermodynamics :

Then

P T
H H
dH dT dP
T P
c c
| | | |
= +
| |
c c
\ . \ .
p
P
V
dH C dT V T dP
T
( c
| |
= +
| (
c
\ .

T P
H V
V T
P T
c c
| | | |
=
| |
c c
\ . \ .
13
From

And

We get
Effect of volume changes on C
v
v
v
E
C
T
c
| |
=
|
c
\ .
T V
E P
T P
V T
c c
| | | |
=
| |
c c
\ . \ .
2
2
v
T
V
C P
T
V T
| | c c
| |
=
| |
c c
\ .
\ .
14
From

And

We get
Effect of pressure changes on C
p
2
2
p
T P
C
V
T
P T
c
| | | | c
=
| |
c c
\ . \ .
p
P
H
C
T
c
| |
=
|
c
\ .
T P
H V
V T
P T
c c
| | | |
=
| |
c c
\ . \ .
15
The Thermodynamic Behavior of Ideal Gases
We have

Form PV = nRT

Thus

Consequently, the internal energy of an ideal gas is independent of the
volume and depends only on the temperature.
T V
E P
T P
V T
c c
| | | |
=
| |
c c
\ . \ .
V
P nR
T V
c
| |
=
|
c
\ .
0
T
E nRT
P
V V
c
| |
= =
|
c
\ .
16
We have

Form PV = nRT

Thus

P
V nR
T P
c
| |
=
|
c
\ .
0
T
H nRT
V
P P
c
| |
= =
|
c
\ .
T P
H V
V T
P T
c c
| | | |
=
| |
c c
\ . \ .
Consequently, the enthalpy of an ideal gas is independent of the pressure and
depends only on the temperature.
17
We have

Form PV = nRT

Thus

P
V nR
T P
c
| |
=
|
c
\ .
0
T
H nRT
V
P P
c
| |
= =
|
c
\ .
T P
H V
V T
P T
c c
| | | |
=
| |
c c
\ . \ .
Consequently, the enthalpy of an ideal gas is independent of the pressure and
depends only on the temperature.
18
From the previous deduction, it must follow also that C
v
and C
p
are functions
of T only and are independent of volume and pressure. Therefore

Furthermore, since for an ideal gas (cE/cV)
T
= 0, then
0
v
T
C
V
c
| |
=
|
c
\ .
0
p
T
C
P
c
| |
=
|
c
\ .
p v
P
V
C C P
T
c
| |
=
|
c
\ .
19
But for an ideal gas

And so we find that

And per mole
P
V
P nR
T
c
| |
=
|
c
\ .
p v
C C nR =
p v
C C R =
This conclusion is the same as obtained from the kinetic theory of gases
20
Isothermal and Adiabatic Processes
Isothermal : any process conducted in a manner such that the temperature
remains constant during the entire operation.

Adiabatic : process in which no heat is absorbed or evolved by the system.

21
For isothermal process

For isothermal and reversible process,
w = w
m
, p = P = nRT/V

or

Isothermal Processes in Ideal Gases
2
1
V
V
q w pdV = =
}
2
1
2
1
ln
V
m
V
dV V
w nRT nRT
V V
= =
}
1
2
ln
m
P
w nRT
P
=
22
For adiabatic process AE = -w.

Any work in an adiabatic process is done at the expense of the internal
energy. As work is performed, the internal energy of the system will
decreases, and consequently the temperature drops.

From the above equation, therefore :

Since P = nRT/V,

Finally,

Adiabatic Processes in Ideal Gases
v
PdV dE nC dT = =
v
nRTdV
nC dT
V
=
/ /
1 1 2 2 1
Cv R Cv R
VT V T C = =
23
A very common form is one involving P and V :

where = C
p
/C
v

or

Adiabatic Processes in Ideal Gases
1 1 2 2
PV PV

=
1 2
2 1
P V
P V
| |
=
|
\ .
24
Exercises
1. A gas expands against a variable opposing pressure given by p = 10/V
atm, where V is the volume of the gas at each stage of the expansion.
Further, in expanding from 10 to 100 liters, the gas undergoes a change
in internal energy of AE = 100 cal. How much heat is absorbed by the gas
during the process ?

2. Two liters of N2 at 0
0
C and 5 atm pressure are expanded isothermally
against a constant pressure of 1 atm until the pressure of the gas is also
1 atm. Assuming the gas to be ideal, what are the values of w, AE, AH,
and q for the process

3. Calculate the work done by 5 moles of an ideal gas during expansion
from 5 atm at 25
0
C to 2 atm at 50
0
C against a constant pressure of 0.5
atm. If for the gas C
p
= 5.0 cal mole
-1
degree
-1
, find also AE, AH, and q for
the process.
25
Exercises
4. Assuming CO
2
to be an ideal gas, calculate the work done by 10 g of CO
2

in expanding isothermally and reversibly from a volume of 5 liters to 10
liters at 27
0
C. What are AE, AH, and q for the process.

5. Two liters of N
2
at 0
0
C and 5 atm pressure are expanded isothermally
and reversibly until the confining pressure is 1 atm. Assuming the gas to
be ideal, calculate of w, AE, AH, and q for the expansion.
26
The Joule-Thomson Effect
V
1
V
2
Porous plug
The situation with real gases

The work done on the system at the left piston is -P
1
V
1
, the work done by
the system at the right piston is P
2
V
2
, and hence the net work done
by the system is
w = P
2
V
2
P
1
V
1
27
Since the process was conducted adiabatically,

AE = - w
E
2
E
1
= - (P
2
V
2
P
1
V
1
)
E
2
+ P
2
V
2
= E
1
+ P
1
V
1
H
2
= H
1
AH = 0

Thus, the process was conducted at constant enthalpy.

The Joule-Thomson coefficient, , is defined as
H
T
P
c
| |
=
|
c
\ .
28
The Joule-Thomson coefficient, , may be thought as of the number of
degrees temperature change produced per atmosphere drop in pressure
under conditions of constant enthalpy.

For a cooling is positive, while for an observed heating is negative.

Example : N
2
, at a pressure such as 200 atm undergoes heating effect at -
150
0
C

, cooling at -100 to 200
0
C.
29
The Joule-Thomson coefficient can be related to other thermodynamic
quantities as follow :

and
p
T
H
C
P
c
| |
=
|
c
\ .
p
P
V
C T V
T
c
| |
=
|
c
\ .
30
The Carnot Cycle
AE
1
= q
2
w
1
AE
2
= w
2
AE
3
= q
1
w
3
AE
4
= w
4
31
The Carnot Cycle
The total change in internal energy for the complete cycle must be

AE = AE
1
+ AE
2
+ AE
3
+ AE
4

= (q
2
q
1
) w
m

Since the system is back to its initial state, we must have AE = 0, hence
w
m
= (q
2
q
1
)

and on division of both sides by q
2
,
2 1
2 2
m
w q q
q q
c

= =
32
The Carnot Cycle
Or in another form
2 1 2 1
2 2 2
m
w q q T T
q q T
c

= = =
33
Exercise
One mole of an ideal gas monoatomic gas is carried through the cycle of
below, consisting of steps A, B, and C and involving states 1, 2, and 3. Fill in
the following table. Assume all of the processes are reversible.
A
B
C
1 2
3
273 546
T,
0
K
22,4
44,8
V,
l/mol
State P, Pa V, liter T, K
1 22,4 273
2 22,4 546
3 44,8 546
Step q, J w, J AE, J
A
B
C
Cycle 0

04 First Law of Thermodynamics

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2011 Imam Siswanto Kimia Fisika I

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