CHE 242: First law of Thermodynamics - Worked Examples

1. One mole of an ideal gas at 300 K is allowed to expand isothermally against a

=
2
1
V
V
ext
dV P w and see if you can obtain = w - 400 J
AND q = + 400 J ; make sure you know how to arrive here

2. Find the work necessary to compress the gas in Example 1 back to its original
volume, using a constant external pressure. Is the process in Example 1
reversible?

Solution:

Before the expansion takes place, the pressure of the gas is:
1
P = 24.9 x 10
5
Pa = 24.9 bar (convince yourself that this is true)
Therefore, to compress the gas back to this pressure, we must use an external
pressure at least 24.9 bar. Thus, we have:

( ) = =
1 2
V V P w
ext
9960 J (convince yourself that this is true)

and the process is not reversible.


3. Find the work done by the gas if the process in Example 1 takes place reversibly.

Solution:
For a reversible isothermal process involving an ideal gas,

= w - 4014 J (make sure you use the correct equation)

Note that the equation describing this reversible is isothermal process involves
only the initial and final volumes. The work done compressing the gas back to V
1

is + 4014 J.

4. Consider an isothermal, reversible expansion of 1 mol of an ideal gas from 12.4 L
at 2.4
o
C to 38.1 L. Calculate q, w, U and H .



Solution:

U = 0 and H = 0 Isothermal change, ideal gas.

Hint:

dT C n U
T
T
V

=
2
1
and dT C n H
T
T
p

=
2
1

What is the value of dT for an isothermal change?



= =
2
1
2
1
V
V
V
V
ext
PdV dV P w ; what is the expression for P for an ideal gas?
There = w -2570.2 J = - 2.57 kJ

To find q, use the First Law of Thermodynamics, w q U + =

q = - w = 2.57 kJ, since U = 0


5. Consider an isobaric compression of 0.450 mol of an ideal gas from 22.4 L and
1.00 atm to 10.5 L. Given that C
p
for the gas is R
2
5
, calculate T , q, w, U and
H .
Solution:

First, to get T , use the ideal gas law to find the initial temperature, and then
Charles law (V/T = constant) to find the final temperature.

1 1 1
nRT V P =
( )( )
( )( ) 314 . 8 450 . 0
10 4 . 22 101325 00 . 1
3
1 1
1

= =
x x
nR
V P
T = 606.3 K
For isobaric (constant pressure) process according to Charles law
2
2
1
1
T
V
T
V
=
2
1
1
2
xV
V
T
T = =
( )
3
3
10 4 . 22
10 5 . 10 3 . 606

x
x
= 284.2 K

3 . 606 2 . 284
1 2
= = T T T = -322.1 K

For a constant pressure process, i.e. dP=0,

( ) T nC T T nC dT nC q H
p p
T
T
p p
= = = =

1 2
2
1

= ( ) ( ) 322 314 . 8
2
5
450 . 0 |

\
|
x
= - 6690 J = - 6.69 kJ

= =
2
1
2
1
V
V
V
V
ext
PdV dV P w , P
ext
= P for reversible expansion/compression

Since P is constant
( ) V P V V P dV P w
V
V
= = =

1 2
2
1
= ( )( )
3 3
10 4 . 22 10 5 . 10 101325 00 . 1

x x x
= 1205 J = 1.21 kJ

Using First law of Thermodynamics

w q U + = = - 6.69 + 1.21 = -5.48 kJ

6. Consider the isochoric ( 0 = V ) process in which the pressure of a 2.35 mol
sample of ideal gas changes from 1.60 atm at 197 K to 2.70 atm. C
V
for the gas is
R
2
3
.

Solution:

First get T using the law of Gay-Lussac, P/T = constant

2
1
1
2
2
2
1
1
xP
P
T
T
T
P
T
P
= = = 70 . 2
60 . 1
197
x = 332 K

197 332
1 2
= = T T T = 135 K

= =
2
1
0
V
V
ext
dV P w , since dV = 0

Using First Law of thermodynamics,
w q U + = or dw dq dU + =

Therefore, dq dU = or q U =

( ) ( ) = |

\
|
= = = = 135 314 . 8
2
3
35 . 2
1 2
x T nC T T nC U q
V V
3956 J = 3.96 kJ

Finally, PV U H + = ( ) PV U H + =
P V U H + = , for constant volume process. So to get the volume:

( )( )
( ) 101325 60 . 1
197 314 . 8 35 . 2
= =
P
nRT
V = 2.376 x 10
-2
m
3
= 23.76 L
( )( ) = + =
3 3
10 101325 60 . 1 70 . 2 10 76 . 23 96 . 3 x x H 6.60 kJ






Practice Problems

1. State briefly the thermodynamic meaning of the terms system, open system,
closed system and isolated system.
2. Each of the following statements is false. Either correct it or state the reason for
its being false.
(a) Heat absorbed at constant volume is called enthalpy.
(b)
p
p
T
U
C |

\
|

=
(c) H, S, P and V are all state functions
(d) The compressibility factor, Z > 1 for most gases observed at high pressure is
attributable to attractive forces
(e) Cp Cv for all liquids and gases
3. For each of the following, state whether w, q, U and H is positive, zero, or
negative, or whether there is insufficient information to decide.
(a) Reversible isothermal expansion of a perfect gas
(b) An ideal gas undergoing a cyclic process
(c) Reversible adiabatic process
(d) Reversible heating at constant volume of an ideal gas
4. Indicate one physical condition under which each of the following formulas
holds:
(a)
P
V
1
for gases
(b) PdV dq dU =
(c)

PV = Constant
(d) dU = 0 (when dV 0)
(e) dH = C
p
dT
5. A gas obeys the equation of state
P RT PV + =
where is a function of T only. Starting with the definition of work done, show
that if the gas is expanded isothermally from V
1
to V
2
, the reversible work will be
(

2
1
ln
V
V
RT w
6. A sample consisting of one mole of monatomic ideal gas (for which R C
v
2
3
= ) is
taken reversibly through the cycle
( ) ( ) ( ) ( ) , , , , ,
1 1 2 2 2 1 1 1
V P A V P C V P B V P A
where P
1
= 1 atm, P
2
=
2
1
P
, V
1
= 22.44 litres and V
2
= 2V
1
, and step ( ) ( ) A C is
carried along an isotherm.
(a) Determine the temperature at ( ) A , ( ) B , and ( ) C .
(b) Determine (in kJ) q, w, U and H for each step and for the overall cycle.