Chemistry 360

Dr. Jean M. Standard

Problem Set 4 Solutions

1. Two moles of an ideal gas are compressed isothermally and reversibly at 298 K from 1 atm to 200
atm. Calculate q, w, U , and H .

For an isothermal reversible expansion of an ideal gas, the work is given by

#V &
w = nRT ln% 2 ( .
$ V1 '

The initial and final volumes are not given. However, for an isothermal process, from the ideal gas equation we
have P1V1 = P2V2 , or

V2 P
= 1.
V1 P2

Substituting, the work can be calculated as

# &
P
w = nRT ln% 1 (
$ P2 '
# 1 atm &
( )
= ( 2 mol) 8.314 J mol1K1 ( 298 K) ln% (
$ 200 atm '
w = 26250 J .

For an ideal gas, the differential of the internal energy is given by dU = C v dT and the differential of the
enthalpy is given by dH = C p dT . Since the process is isothermal, dT = 0 , and so dU = 0 and dH = 0 .

Therefore,
H = 0.
U = 0 and

Finally, from the First Law of thermodynamics, U = q + w . Since U = 0 ,
q = w = 26250 J .

Summary of results:

q 26250 J
w 26250 J
U 0J
H 0J

 2
2. A balloon filled with 0.505 mol of gas contracts reversibly from 1.0 L to 0.10 L at a constant temperature
of 5.0C. It simultaneously loses 1270 J of heat. Calculate q, w, U , and H for the process.

For an isothermal reversible expansion of an ideal gas, the work is given by

# &
V
w = nRT ln% 2 ( .
$ V1 '

Substituting, the work can be calculated as

# &
V
w = nRT ln% 2 (
$ V1 '
# 0.10 L &
( )
= ( 0.505 mol) 8.314 J mol1K1 ( 278.15 K) ln%
$ 1.0 L '
(

w = 2690 J .

Even though the process described is isothermal, the overall internal energy change is not zero since the
problem indicates that at the same time as the isothermal compression, heat is removed from the system. So,
be employed in order to determine U . The problem states that q = 1270 J , so the First
the First Law must
Law yields

U = q + w

= 1270 J + 2690 J
U = 1420 J .

Finally, to determine the enthalpy change H the definition of enthalpy may be used,
H = U + PV
H = U + ( PV ) .

In order to determine the change ( PV ) = P2V2 P1V1 , the volumes are given but the pressures are not. So, the
ideal gas equation may be employed
to determine the initial and final pressures,
nRT
P1 =
V1

( 0.505mol)( 0.08205L atm mol1K 1)( 278.15K)

=
(1.0 L)
P1 = 11.525atm.

and
nRT
P2 =
V2

( 0.505mol)( 0.08205L atm mol1K 1)( 278.15K)

=
( 0.1L)
P2 = 115.25atm.

 3
2. Continued

Now the change ( PV ) may be determined,

( PV ) = P2V2 P1V1
= (115.25atm)( 0.1L) (11.525atm)(1.0 L)
( PV ) = 0.

It should not be a surprise that the factor ( PV ) equals 0 since for an ideal gas another way to write this is

( PV ) = ( nRT )
( PV ) = nR T .

Since the temperature is constant, T = 0 and as shown above, ( PV ) = nRT = 0 . The enthalpy change is
therefore given by

H = U + ( PV )

= U
H = 1420 J.

Summary of results:

q 1270 J
w 2690 J
U 1420 J
H 1420 J

3. The temperature dependence of the molar constant pressure heat capacity of a real gas may be
represented by the function

C p,m = + T + T 2 .

1 1
where , , and are constants. For N2, these constants have the values = 26.984 J K mol ,
= 5.910 103 J K2 mol1 , and 7 3 1
= 3.377 10 J K mol . Determine the amount of heat required to
raise the temperature of 1 mol of N2 gas from 300 to 1000 K at constant pressure.

In this problem, we know that the heat at constant pressure is the enthalpy, dq p = dH .

The exact differential of enthalpy is

# H &
dH = C p dT + % ( dP .
$ P 'T

 4
3. Continued

At constant pressure, dP = 0 , so the exact differential of enthalpy reduces to

dH = C p dT .

On a molar basis, this equation becomes
dH m = C p,m dT .

Integrating,

H 2,m T2
H 1,m
dH m = C dT
T1
p,m

T2
H m = ( + T
T1
+ T 2 dT )

(
H m = (T 2 T1) + 2 T 22 T12 + 3 T 23 T13 . )
( )
Substituting the values of the parameters, we have

H m = (T 2 T1) +

2 (T 2
2
)
T12 +

3 (T 3
2 T1
3
)
(
H m = 26.984 J mol1K1 (1000 K 300 K) )
+ 1
2 (5.910 10 J mol K ) (*)(1000 K) (300 K) +-,
3 1 2 2 2

+ 1
3 (3.377 10 J mol K ) (*)(1000 K) (300 K) +-,
7 1 3 3 3

= 18889 J/mol + 2689 J/mol 110 J/mol

H m = 21468 J/mol.

Thus, at constant pressure,

q p,m = H m = 21468 J/mol.

4. Estimate the final temperature of one mole of gas at 200.0 atm and 19.0C as it is forced through a porous
plug to a final pressure of 0.95 atm. The Joule-Thomson coefficient of the gas is 0.150 K/atm.

The Joule-Thomson coefficient JT is defined as

# T &
JT = % ( .
$ P 'H

Since the problem requests an estimate of the final temperature, we can approximate the derivative in the
following way,

# T & T
JT = % ( .
$ P 'H P

Note that in the equation above we have approximated infinitesimal changes by finite changes.

 5
4. Continued

We can solve the expression for the temperature difference T ,

T
JT
P
or T = JT P .

Substituting the numerical values,

T = JT ( P2 P1)
= ( 0.150 K/atm)( 0.95atm 200.0 atm)
T = 29.86 K .

The final temperature then may be determined,

T = T 2 T1 = 29.86 K
or T 2 = T1 29.86 K
T 2 = 292.16 K 29.86 K
T 2 = 262.29 K or 10.9! C .

So for a pressure drop of nearly 200 atm, the temperature of this particular gas drops by nearly 30 degrees.

5. Determine the final temperature of 0.122 mol of an ideal monatomic gas that performs 75 J of work
adiabatically if the initial temperature is 235C.

For an adiabatic process, q=0, so from the First Law,

U = q + w
U = w .

Now we are given the amount of work done and need to determine the final temperature. For an ideal gas, we
can develop an expression for U in order to determine the temperature,

dU = C v dT (for an ideal gas)
U2 T2
U 1
dU = T1
C v dT
T2
U = C v T1
dT

U = C v T .

Note that this expression requires that the constant volume heat capacity is independent of temperature in order
to pull it out of the integral.

So, for an adiabatic process involving an ideal gas, we have

U = w = C v T .

 6
5. Continued

In order to evaluate this expression, we need the constant volume heat capacity. Any gas, monatomic,
diatomic, or polyatomic, may behave ideally. Because these gases have different numbers of degrees of
freedom, they also have different heat capacities. It is indicated in this problem that the ideal gas is monatomic.
For such a gas, we know that the constant volume heat capacity is

Cv = 3 nR .
2

Substituting,

U = w = C v T
= 3 nR T .
2

We can now solve this equation for the temperature difference,

2w
T =
3nR
2 ( 75J )
=
3 ( 0.122 mol)(8.314 J/molK)
T = 49.29 K .

Note that the work is negative because the system performs work on the surroundings. The initial temperature
is 235C or 508.15 K. Solving for the final temperature, we have

T = T 2 T1 = 49.29 K
or T 2 = T1 49.29 K
T 2 = 508.15K 49.29 K
T 2 = 458.86 K or 185.7! C .

6.
A tank contains 20 L of compressed nitrogen at 10 atm and 25C. Calculate the work when the gas is
allowed to expand reversibly and adiabatically to 1 atm pressure. Assume that the gas behaves ideally.

For an adiabatic process, we know that q = 0 . From the First Law, U = q + w . With q = 0 , we have

w = U .

of the internal energy is given

For an ideal gas, the differential by dU = C v dT
. Integrating,
U2 T2
U 1
dU = T
1
C v dT .

Assuming that C v is independent of temperature, the integration yields

w = U = C v (T 2 T1) .

In order to calculate the work, the initial and final temperatures are required. However, only the initial
temperature is given. The final temperature must be determined from the initial temperature, the initial volume,
and the initial and final pressuresin the adiabatic expansion.
 7
6. Continued

For a reversible adiabatic process, we derived in class that

"T % "V %
C v ln$ 2 ' = nR ln$ 2 ' .
# T1 & # V1 &

Using properties of logarithms, we have

" T %C v " V %nR
ln$ 2 ' = ln$ 2 ' .
# T1 & # V1 &

Taking the exponential of both sides yields

" T %C v " V %nR
$ 2' = $ 2' ,
# T1 & # V1 &

Cv
or " T 2 % " V %nR
$ ' = $ 1' .
# T1 & # V2 &

nRT
For an ideal gas, V = , so the ratio of volumes on the right hand side of the equation can be rewritten to
P
give

" T %C v " T P %nR

2 = $ 1 2' .
$ '
# T1 & # T 2 P1 &

Rearranging to get the temperatures on the left,

" T %C v " T %nR " P %nR
2 2 = $ 2'
$ ' $ '
# T1 & # T1 & # P1 &
" T %C v +nR " P %nR
2 = $ 2'
$ '
# T1 & # P1 &
nR
T2 " P % C +nR
= $ 2' v .
T1 # P1 &

Solving for the final temperature,

nR
" P % C +nR
T2 = T1 $ 2 ' v ,
# P1 &
nR
" P %C
T2 = T1 $ 2 ' p .
# P1 &

 8
6. Continued

Note that nitrogen is not a monatomic ideal gas, so we need the actual heat capacity of nitrogen gas. From the
1 1
CRC we have that C p,m = 29.125 J mol K . Therefore, the exponent is

nR nR R
= =
Cp nC p,m C p,m

8.314 J mol1K1
=
29.125J mol1K1
nR
= 0.28546.
Cp

The final temperature is

" P %0.28546
T2 = T1 $ 2 '
# P1 &
" 1 atm %0.28546
= ( 298.15 K) $ '
# 10 atm &
T2 = 154.52 K .

Now, the work and internal energy change can be calculated using the relation
w = U = C v (T 2 T1)
= nC v,m (T 2 T1) .

Since C p = C v + nR , in terms of molar quantities, we have C p,m = C v,m + R . We can solve for C v,m
to get

C v,m = C p,m R

= 29.125J mol1K1 8.314 J mol1K1
C v,m = 20.811J mol1K1.

The moles of nitrogen gas can be calculated from the initial state,
P1V1
n =
RT1

=
(10 atm)( 20 L)
(0.08205 L atm mol 1 1
K )(298.15 K)
n = 8.176 mol.

Substituting,
w = U = nC
v,m (T 2 T1 )

( )
= (8.176 mol) 20.811J mol1K1 (154.52 K 298.15K)
w = U = 24440 J .