Chemistry 360

Spring 2015
Dr. Jean M. Standard
February 11, 2015

Name ____________KEY_______________

Exam 1 Solutions 100 points

1.) (14 points) The temperature dependence of the molar constant pressure heat capacity of CH 4 gas may be
represented by the function

C p,m = + T +

,
T2

where , , and are constants. For CH4, these constants have the values = 20.25J K 1mol1 ,

= 0.01535J K 2 mol1 , and = 1.142 10 6 J Kmol1 .

3.0 moles of CH4 gas are heated reversibly from 500 to 1000 K at a constant pressure of 1.0
In this case,
bar. Calculate H (in Joules) for the process.
The exact differential of enthalpy is

" H %
dH = C p dT +$
' dP.
# P &T
At constant pressure, the second term drops out to yield

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

dH = nC p,m dT .
Integrating,
H2

T2
dH = nC p,m dT
T1

H = n

T2
T1

#
&
% + T + 2 ( dT
$
T '

1
dT
T2
# 1
n 2
1&
H = n (T2 T1 ) +
T2 T12 + n % + (.
2
$ T2 T1 '
= n

T2

T1

dT +n

T2

T1

T dT +n

T2

T1

2
1.

Continued
Substituting the values of the parameters, we have

H = n (T2 T1 ) +

# 1
n 2
1&
T2 T12 + n % + (
2
$ T2 T1 '

H = (3.0 mol) 20.25J mol1K 1 (1000 K 500 K )

1
2
2
(3.0 mol) 0.01535J mol1K 2 (1000 K ) (500 K )
2
#
1
1 &
+ (3.0 mol) 1.142 10 6 J Kmol1 %
+
(
$ 1000K
500K '

)(

= (3.0 mol) (10125J/mol 5756 J/mol + 1142 J/mol)

H = 16532 J.

3
2.) (14 points) Sketch a plot of the isotherms of an ideal gas on a P - Vm graph. Make sure to show at least
three isotherms, and label them in terms of high and low temperatures. In a sentence or two, compare
the ideal gas isotherms to real gas isotherms, and explain for which temperatures the ideal and real gases
would be expected to exhibit similar isotherms. Also discuss
whether or not the ideal gas exhibits critical

behavior and how this would be evident on the P - Vm graph.

The isotherms of an ideal gas are shown below. The high temperature isotherms are positioned further out from
the x- and y-axes, while the low temperature isotherms are closer to the axes as indicated. All the isotherms of

an ideal gas are hyperbolic in shape.

The isotherms at high temperature would be those that would be expected to be similar for both real gases and
ideal gases. Isotherms at low temperature tend to deviate from ideal behavior for real gases.
Critical behavior, meaning the existence of a critical point, would be evident on the isotherm graph as an
inflection point. At temperatures below this point, the liquid phase would exist. For an ideal gas, no inflection
point is observed in any of the isotherms; thus, the ideal gas does not exhibit critical behavior and does not
condense to form a liquid.

4
3.) (14 points) An equation of state which describes the stretching of a rubber band is given by

F
=CT .
L L0
Here, F is the tension of the rubber band, L is the length of the rubber band, L0 is a constant equal to the
unstretched length, T is temperature, and C is also a constant. Starting from the definition of work,
w = F dL , derive an expression for the work done in a reversible isothermal expansion from length

L1 to L2 at temperature T.
We can obtain an expression for the tension F from the equation of state given above. Solving the equation for
F yields

F
=CT
L L0
F =CT ( L L0 ) .
Substituting this relation into the equation for work gives
L2

w = F dL
L1

L2

w = CT ( L L0 ) dL
L1

L2

L2

w = C TL dL C L0 T dL .
L1

L1

Since the process is isothermal, T can be pulled out of the integrals to give
L2

L2

w = CT L dL C TL0 dL .
L1

L1

Integrating leads to the result

" L2
L2 %
w=CT $ 2 1 'C TL0 ( L2 L1 ) .
2&
#2

5
4.) (15 points) True/false, short answer, multiple choice.
a.) True or False : The compression factor Z of a real gas approaches 1 at very high pressures.

b.) True or False: A gas with a positive Joule-Thomson coefficient JT may be used as a refrigerant.

c.) Short answer

The _____heat capacity_____ is a quantity that provides a measure of the ability of a substance to store
energy.

d.) Short answer

An _____extensive______ variable scales with the size of the system.

e.) Multiple Choice. The Equipartition Theorem predicts that the molar heat capacity at constant volume of an
ideal monatomic gas has the following form.

1) Cv,m =

5
RT.
2

2) Cv,m =

3
RT.
2

3) Cv,m =

3
R.
2

4) Cv,m =

5
R.
2

6
5.) (14 points) An equation of state for a real gas is given by

Z = 1+

bP
aP
2 3 ,
RT
R T

where a and b are constants and Z is the compression factor.

a.) Develop an expression for the isothermal compressibility,

1 % V (
'
* .
V & P )T

To evaluate the partial derivative, we have to solve the equation of state for V,

bP
aP
2 3 ,
RT
R T
PVm
bP
aP
= 1+
2 3
RT
RT
R T
Z = 1+

or
RT
Multiplying both sides by P yields

RT
P
RT
=
P

Vm =

Vm

#
bP
aP &
2 3(
%1 +
RT
$
R T '
a
+ b
.
RT 2

Writing the expression in terms of volume rather than molar volume gives

V =

nRT
na
+ nb
.
P
RT 2

Evaluating the partial derivative required for the isothermal compressibility,

# V &
nRT
%
( = 2

P
$
'T
P

Evaluating the isothermal compressibility,

1 % V (
'
*
V & P )T

1 % nRT (
'
*
V & P2 )
nRT
= 2
.
P V
=

Further simplification is not necessary in this case.

7
3.

Continued
b.) Develop an expression for the thermal expansion coefficient,

1 $ V '
&
) .
V % T (P

Using the same expression for the volume developed for part (a) we have,

nRT
na
+ nb
.
P
RT 2

V =

Evaluating the partial derivative required for the thermal expansion coefficient,

# V &
nR
2na
+
.
%
( =
P
$ T 'P
RT 3

Evaluating the thermal expansion coefficient,

1
V

$ V '
&
)
% T (P

1 $ nR
2na '
+
&
)
V%P
RT 3 (
nR
2na
=
+
.
PV
RT 3V
=

Further simplification is again not necessary in this case.

8
6.) (14 points) Determine the quantities q, w, U, and H for the following processes involving one mole of
an ideal monatomic gas. Express your results in Joules.
a.) a reversible process at constant pressure with T1 = 200 K, T2 = 500 K, and a final volume of V2 = 800
mL.
We can start with the basic definition of work,

w =

Pext dV .

For a reversible process, the external pressure equals the pressure of the gas, Pext = P , so the expression
for the work becomes

w =

P dV .

Since the pressure is constant, we can pull it out of the integral and integrate from V1 to V2 ,

w = P

V2
V1

dV

w = P(V2 V1 ) .
We are given the final volume, but not the initial volume or the pressure. However, since we know the
temperatures, we can use the ideal gas equation to determine the pressure from the final volume and

temperature.

P=
=

nRT2
V2

(1 mol) (0.08206 Latm/molK ) (500 K )

(0.800 L )

P = 51.29 atm.
Now that we know the pressure, we can get the initial volume, also from using the ideal gas equation.

nRT1
P
1 mol) ( 0.08206 Latm/molK ) ( 200 K )
(
=
(51.29 atm )

V1 =

V1 = 0.320 L.
Finally, the constant pressure work can be calculated.

w = P (V2 V1 )
= ( 51.29 atm ) ( 0.800 L 0.320 L )
" 101.3 J %
= 24.62 Latm $
'
# 1 Latm &
w = 2490 J

9
6 a.)

Continued
To determine the internal energy change, we can start with the exact differential for an ideal gas and
integrate,

dU = C v dT
U2

dU =

T2

U = C v

C v dT
T2

dT

U = C v T .
Note that here we have used that the heat capacity of an ideal gas is constant. Finally, we can substitute the
initial and final temperatures, and
use the information that the constant volume heat capacity of an ideal
monatomic gas equals 3/2nR.

U = Cv T
3
nRT
2
3
= (1 mol) (8.314 J/molK ) ( 500 200 K )
2
U = 3740 J
=

The change in enthalpy may be calculated in a similar way, this time using the information that the constant
pressure heat capacity of an ideal monatomic gas equals 5/2nR.

H = C p T
5
nRT
2
5
= (1 mol) (8.314 J/molK ) ( 500 200 K )
2
H = 6240 J
=

Finally, the heat may be calculated using the First Law, or by noting that at constant pressure the heat
absorbed or lost is equal to the enthalpy change,

q p = H = 6240 J.

10
6.

Continued
b.) a reversible isochoric process with a volume of 800 mL with P1 = 1.0 bar and P2 = 5.0 bar.
We can start with the basic definition of work,

w =

Pext dV .

For a reversible process, the external pressure equals the pressure of the gas, Pext = P , so the expression
for the work becomes

w =

P dV .

Since the volume is constant, the differential dV = 0, and therefore

w = 0.

To determine the internal energy change, we can use the same form as in part (a),

U = Cv T .
We are not given the initial or final temperatures. However, since we know the volume and pressures, we
can use the ideal gas equation to determine the temperatures.

T1 =
=

P1V
nR

(1.0 bar ) (0.800 L )

(1 mol) (0.08314 Lbar/molK )

T1 = 9.62 K.

T2 =
=

P2V
nR

(5.0 bar ) (0.800 L )

(1 mol) (0.08314 Lbar/molK )

T2 = 48.11 K.
Next, we can substitute the initial and final temperatures, and use the information that the constant volume
heat capacity of an ideal monatomic gas equals 3/2nR.

U = Cv T
3
nRT
2
3
= (1 mol) (8.314 J/molK ) ( 48.11 9.62 K )
2
U = 480 J
=

11
6 b.

Continued
The change in enthalpy may be calculated in a similar way, this time using the information that the constant
pressure heat capacity of an ideal monatomic gas equals 5/2nR.

H = C p T
5
nRT
2
5
= (1 mol) (8.314 J/molK ) ( 48.11 9.62 K )
2
H = 800 J
=

Finally, the heat may be calculated using the First Law,

q=U w
=4800
q=480J.

12
7.) (15 points) True/false, short answer, multiple choice.
a.) True or False : If a function possesses a differential that is said to be exact, then it is path dependent.

b.) True or False: A gas with a positive Joule-Thomson coefficient JT may be used as a refrigerant.

c.) Short answer

A ________reversible_______ process is one in which any changes to the system are made very slowly
so that equilibrium is maintained.

d.) Short answer

The ____universe_________ corresponds to the combination of system and surroundings.

e.) Multiple Choice: Circle the correct result for an isothermal reversible expansion of an ideal monatomic
gas.
1) w = 0 , q 0 , U = q .
2) w 0 , q = 0 , U = w .

3) w 0 , q = w , U = 0 .

4) w = 0 , q = 0 , U = 0 .