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Determine the amount of pressure-volume work performed by 1 mole of water freezing to ice at 0C and
1 atm pressure. The density of liquid water at 0C is 0.99984 g/mL and the density of ice is 0.91680
g/mL.
Going from liquid water to ice involves a volume change, so PV work must be determined. The definition of
work w is
w =
Pext dV .
At constant pressure (standard, 1 atm), we can pull the pressure out of the integral and integrate the volume
from the initial to the final value,
w = Pext
V2
dV
" mL %
V1 = (1 mol)(18.015 g/mol)$
'
# 0.99984 g &
V1 = 18.018 mL = 0.018018 L .
For 1 mole of ice, the volume is
" mL %
V2 = (1 mol)(18.015 g/mol)$
'
# 0.9168 g &
V2 = 19.650 mL = 0.019650 L .
2
2.
One of the primary components of nuclear fuel rods is uranium(IV) oxide, UO2. The melting point of
UO2 is 3140 K and the enthalpy of fusion is 70.0 kJ/mol. Determine the enthalpy change per mole for the
process
UO 2 (s, 3100 K )
UO 2 ( , 3200 K ) .
The molar heat capacities are C p,m (s) = 211.0J mol1K 1 and C p,m ( ) = 134.2J mol1K 1 . Assume 1 bar
pressure and that the molar heat capacities of solid and liquid UO2 are independent of temperature.
For a physical change involving heating/cooling and/or phase transitions, we can break the process up into steps
and then calculate the enthalpy changes for each of the steps. The overall enthalpy change is then just the sum
of the enthalpy changes for the steps since H is a state function. For this particular process, the steps are:
UO 2 (s, 3100 K )
UO 2 (s, 3140 K ) .
UO 2 (s, 3140 K )
UO 2 ( , 3140 K ) .
UO 2 ( , 3140 K )
UO 2 ( , 3200 K ) .
The overall molar enthalpy change for the process is then just equal to the sum of the molar enthalpy changes
for each of the steps,
# H &
dH = C p dT + %
( dP .
$ P 'T
Since the process occurs at constant pressure, dP = 0 , the expression becomes
dH = C p dT .
Integrating in order to calculate the enthalpy change for the heating process from T1 to T 2 ,
H =
T2
C p dT .
If we assume that the heat capacity is independent of temperature, then we can integrate to get
H = C p (T 2 T1) .
Expressing this relation in terms of molar quantities, we divide both sides by the number of moles to give
H m = C p,m (T2 T1 ) .
3
2.) Continued
For the steps involving phase transitions, the enthalpy change is just the moles of substance multiplied by the
standard molar enthalpy change (in this case, fusion),
H m = H !fus .
Using these expressions, the enthalpy changes for each of the steps may be calculated.
Step 1
In this step, solid UO2 is heated from 3100 K to the transition temperature of 3140 K. Substituting the
appropriate heat capacity value and temperatures, we have
H 2,m = H !fus
= ( 70.0 kJ/mol)
H 2 = 70000 J/mol .
Step 3
In this step, liquid UO2 is heated from the transition temperature of 3140 K to 3200 K. Substituting the
appropriate heat capacity value and temperatures, we have
4
3.
Determine the enthalpy change for one mole of water undergoing the following transformation,
H 2O s, 30! C
H 2O g, 300! C .
The pressure is constant at 1 bar, and assume that the molar heat capacities are independent of
temperature.
For a physical change involving heating/cooling and/or phase transitions, we can break the process up into steps
and then calculate the enthalpy changes for each of the steps. The overall enthalpy change is then just the sum
of the enthalpy changes for the steps. For this particular process, the steps are:
(1)
H 2O s, 30! C
H 2O , 0! C .
)
( 3) heating liquid water from 0 C to 100 C, H O (, 0 C) H O (, 100 C) .
( 4) phase transition from liquid to gas at 100 C, H O (, 100 C) H O ( g, 100 C) .
( 5) heating gaseous water from 100 C to 300 C, H O ( g, 100 C) H O ( g, 300 C) .
( 2)
H 2O s, 0! C .
The overall enthalpy change for the process is then just equal to the sum of the enthalpy changes for each of the
steps,
H = H 1 + H 2 + H 3 + H 4 + H 5 .
In order to calculate the enthalpy changes for each of the steps, the molar heat capacities for all three phases are
required, along with the molar enthalpies of fusion and vaporization. These values are available from standard
reference sources such as your textbook, the CRC, or the NIST Webbook, and are tabulated below.
C p,m
Substance
(Jmol K )
H2O (s)
H2O (l)
H2O (g)
36.2
75.3
33.6
H R!
Phase change
for H2O
(kJ/mol)
6.01
44.0
fusion
vaporization
The steps listed above can be divided into two types: heating steps and phase transition steps. For the heating
steps, we can begin with the exact differential for H,
# H &
dH = C p dT + %
( dP .
$ P 'T
Since the process occurs at constant pressure, dP = 0 , the expression becomes
dH = C p dT .
Integrating in order to calculate the enthalpy change for the heating process from T1 to T 2 ,
H =
T2
C p dT .
5
3.) Continued
If we assume that the heat capacity is independent of temperature, then we can integrate to get
H = C p (T 2 T1) .
Expressing this relation in terms of the molar heat capacity, we have
H = nC p,m (T 2 T1) .
For the steps involving phase transitions, the enthalpy change is just the moles of substance multiplied by the
the phase transition,
standard molar enthalpy change for
H = nH !phasechange .
Using these expressions, the enthalpy changes for each of the steps may be calculated.
Step 1
In this step, solid water is heated from 30C to the transition temperature of 0C. Substituting the appropriate
heat capacity value and temperatures, we have
H 2 = nH !fus
= (1 mol)( 6.01 kJ/mol)
H 2 = 6010 J .
Step 3
In this step, liquid water is heated from 0C to the transition temperature of 100C. Substituting the appropriate
Substituting appropriate
standard molar enthalpy change, we have
!
H 4 = nH vap
6
3.) Continued
Step 5
Finally, in this step, gaseous water is heated from 100C to the final temperature of 300C. Substituting the
appropriate heat capacity value and temperatures, we have
steps,
H = H 1 + H 2 + H 3 + H 4 + H 5 .
Substituting, we have
H = H1 + H 2 + H 3 + H 4 + H 5
= 1090 + 6010 + 7530 + 44000 + 6720 J
H = 65350 J
or
65.35 kJ .
7
4.
Metabolic activity in the human body releases about 110 kJ of heat per day. Since the body is made up
of mostly water, approximate a body as consisting of 50 kg of water.
(a) How fast would the body temperature rise (in degrees K/day) if the body is considered to be an
isolated system at constant pressure (1 bar)? The molar heat capacity of liquid water is
C p,m = 75.291J mol1K1 .
Since the process occurs at constant pressure,
q p = H =
T2
C p dT .
If we assume that the heat capacity of the body (i. e., the 50 kg of water) is independent of temperature,
then we can integrate to get
heat is produced per day, and we know the number of moles of water in 50 kg is
We are told how much
" 1000 g %" 1 mol %
'$
' = 2775 mol.
# 1 kg &# 18.015 g &
( 50 kg)$
We need to figure out the temperature change. Solving the equation above for the temperature difference,
q p = nC p,m T
or T =
qp
nC p,m
Substituting,
T =
q
p
nC p,m
1 10 7 J
T = 48 K .
Thus, the temperature rise per day is T = 48 K per day.
(b) How much water in kg per day must the body eliminate as perspiration to maintain normal body
temperature of 98.6F? Assume that the energy required to vaporize water is 2.41 kJ/g.
4
To maintain a constant body temperature of 98.6F, the body would have to eliminate 1 10 kJ of heat per
day. If this were done by using the heat generated to vaporize water, each g of water would require 2.41 kJ
of heat. Thus, the amount of water vaporized per day would be
1 10 4 kJ
= 4150 g.
2.41kJ/g
In other words, 4.15 kg of water would be vaporized as perspiration every day in order to maintain constant
body temperature!
8
5.
Consider the following compounds: NaHCO3 (s) , Na 2CO3 (s) , CO 2 (g) , and H 2O ( ) .
(a) Write out the formation reactions for each of the compounds listed above.
The formation reaction of NaHCO3 (s) is
Na (s) +
1
2
H 2 ( g) + C (s) +
3O
2 2
( g)
( g)
Na 2CO 3 (s) .
NaHCO 3 (s) .
2 Na (s) + C (s) +
3O
2 2
C (s) + O 2 ( g) CO 2 ( g) .
1O
2 2
H 2 ( g) +
( g)
H 2O ( ) .
(b) Show that the formation reactions for the compounds listed above may be combined to produce an
overall reaction given by
2 NaHCO3 (s)
Now we have to take the formation reactions from part (a) in the appropriate combination to form the
overall reaction given here. Taking twice the reverse of the first reaction and adding all the others yields
[ NaHCO 3 (s)
Na (s) +
2 Na (s) + C (s) +
3O
2 2
1
2
( g)
C (s) + O 2 ( g) CO 2 ( g)
H 2 ( g) + 12 O 2 ( g) H 2O ( )
2 NaHCO 3 (s)
H 2 ( g) + C (s) +
3O
2 2
( g) ]
Na 2CO 3 (s)
Na 2CO 3 (s) + CO 2 ( g) + H 2O ( )
9
5.) Continued
(c) Use values of standard enthalpies of formation from the CRC or NIST to calculate H R! in kJ/mol at
25C for the reaction given in part (b).
The standard enthalpies of formation at 25C as obtained from the CRC are:
H !f
Compound
(kJ/mol)
NaHCO3 (s)
Na2CO3 (s)
950.81
1130.77
CO2 (g)
393.51
H2O (l)
285.83
10
6.
( a)
( b)
( c)
H 2 ( g) +
1O
2 2
CH 3OH ( ) +
( g)
H 2O ( g)
3O
2 2
( g)
CO 2 ( g) + 2 H 2O ( g)
H 2 ( g) + F2 ( g) 2 HF ( g) .
(a) Using values from the tables in the Appendix of your textbook, calculate the molar enthalpies of
reaction at 25C for each of these reactions. Convert your results to units of kJ per total mass of
H R! = H !f ( H 2O, g) H !f ( H 2 ) 12 H !f (O 2 )
= 241.8kJ/mol 0 0
H R!
= 241.8kJ/mol.
Expressing this per kg of reactants, the weight of 1 mole of H2 and 1/2 mole of O2 is 18.015 g, or 0.018015
kg. Thus,
# 1molreactants &
H R! = (241.8kJ/mol) %
(
$ 0.018015kg '
H R! = 13420 kJ/kg reactants.
Expressing this per kg of reactants, the weight of 1 mole of CH3OH and 3/2 mole of O2 is 80.041 g, or
0.080041 kg. Thus,
# 1molreactants &
H R! = (637.9 kJ/mol) %
(
$ 0.080041kg '
H R! = 7970 kJ/kg reactants.
H R! = 2 H !f ( HF ) H !f ( H 2 ) H !f ( F2 )
= 2 (273.3kJ/mol) 0 0
H R! = 546.6 kJ/mol.
11
6
a). Continued
Expressing this per kg of reactants, the weight of 1 mole of H2 and 1 mole of F2 is 40.012 g, or 0.040012
kg. Thus,
# 1molreactants &
H R! = (546.6 kJ/mol) %
(
$ 0.040012 kg '
H R! = 13661kJ/kg reactants.
(b) Since the thrust in a rocket is greater when the molar mass of the exhaust gas is lower, divide the
absolute enthalpy per kilogram by the average molar mass of the products. Arrange the reactions in
order of effectiveness on the basis of thrust. What is the most effective reaction?
The thrust T is the absolute enthalpy per kilogram divided by the average molecular weight of the products.
For reaction (a), H 2 ( g) + 12 O 2 ( g) H 2O ( g) , the thrust T is
T=
H R! ( kJ/kg)
M products
13420 kJ/kg
0.001801kg/mol
T=
=
H R! ( kJ/kg)
M products
1
3
7970 kJ/kg
0.04401kg/mol
(
) + 23 (0.01801kg/mol)
T=
=
H R! ( kJ/kg)
M products
13661kJ/kg
0.02001kg/mol
12
7.
(a )
( b)
( c)
1O
2 2
(g )
H 2 O ( )
H R! = 393.5kJ/mol
H R! = 285.5kJ/mol
H R! = 3119.6 kJ/mol.
Using these reactions in conjunction with Hess' Law to determine the enthalpy of formation of ethane.
The formation reaction of ethane is
2C (s, graphite) + 3H 2 ( g) C 2 H 6 ( g) .
Note that reaction (a) above contains graphite as a reactant; the reaction must be doubled, though, since the
formation reaction involves 2 moles of graphite. Also, reaction (b) contains hydrogen gas as a reactant; this
reaction must be multiplied by a factor of 3 to match the molar ratio needed in the formation reaction. Finally,
reaction (c) involves ethane, but as a reactant; thus, the reverse of reaction (c) is required, multiplied by 1/2 to
get the correct stoichiometry:
2 [C ( graphite) + O 2 ( g) CO 2 ( g)]
3 H 2 ( g) + 12 O 2 ( g) H 2O ( )
1
2
[4 CO 2 (g)
+ 6 H 2O ( ) 2C 2 H 6 ( g) + 7O 2 ( g)]
2C ( graphite) + 3H 2 ( g) C 2 H 6 ( g)
From the combination of reactions, the enthalpy of formation of ethane can be calculated from Hess' Law,
H !f = 2 H R! ( a ) + 3H R! ( b) 12 H R! ( c )
= 2 (393.5kJ/mol) + 3 (285.5kJ/mol) 12 (3119.6 kJ/mol)
H !f = 83.7kJ/mol.
13
8.
The combustion of 0.4862 g naphthalene in a constant volume bomb calorimeter caused a temperature
rise in the water bath of 1.707C. The final temperature was 298.00 K. The heat capacity of the
calorimeter was 10290 J/K.
(a) Determine the molar internal energy of combustion of naphthalene and its molar enthalpy of
combustion.
Using the bomb calorimeter equation developed in class,
U comb = C v,cal T
= (10290 J/K)(1.707 K)
U comb = 17565J .
To get the molar internal energy of combustion, we divide by the number of moles of naphthalene.
U comb
n
17565 J
=
$ 0.4862 g '
&
)
% 128.174 g/mol (
U comb,m =
= 4.6306 10 6 J/mol
or U comb,m = 4.6306 10 3 kJ/mol.
Finally, to get the molar enthalpy of combustion, we use
For this conversion, the balanced reaction for the combustion of naphthalene is required,
C 10 H 8 (s) + 12 O 2 ( g) 10 CO 2 ( g) + 4 H 2O ( ) .
From the balanced reaction, the change in number of moles of gas is
n gas = 10 12
n gas = 2 .
Substituting,
H comb,m = U
comb,m + n gas RT
14
8.
Continued
(b) Using the results from part (a), calculate the enthalpy of formation of naphthalene.
The formation reaction of naphthalene is
10 CO 2 ( g) + 4 H 2O ( ) C 10 H 8 (s) + 12 O 2 ( g) .
We can use this to construct the formation reaction, along with the formation reactions for water and
carbon dioxide,
10 CO 2 ( g) + 4 H 2O ( ) C 10 H 8 (s) + 12 O 2 ( g)
( g) H 2O ( )]
10 [C ( graphite) + O 2 ( g) CO 2 ( g)]
10 C ( graphite) + 4 H 2 ( g) C 10 H 8 (s)
4
[H 2 (g)
1O
2 2
Thus, we see that the enthalpy of formation of naphthalene is equal to 4 times the enthalpy of formation of
water, plus 10 times the enthalpy of formation of carbon dioxide, minus the enthalpy of combustion of
naphthalene,
(C10 H 8 )
= 442.6 kJ/mol.
15
9.
A sample of solid KNO3 (1.668 g) is dissolved in 100 mL of water initially at 24.85C in a constant
pressure solution calorimeter. The final temperature was 23.76C. Assume the constant pressure heat
capacity of the calorimeter is 101.3 cal/K. Determine the molar enthalpy of solution of KNO3.
Using the calorimeter equation for solution calorimetry,
H soln = C p,cal T
= (101.3cal/K)( 23.76 24.85K)
H soln = 110.4 cal.
To get the molar enthalpy of solution, we divide by the number of moles of KNO3,
H soln
n
110.4 cal
=
# 1.668 g &
%
(
$ 101.10 g/mol '
H soln,m =
= 6692 cal/mol
or H soln,m = 6.69 kcal/mol.
16
10. Using the values in the table below, reported at 25C, determine H R! at 500C for the reaction
CH 3OH ( ) CH 4 ( g) +
1
O
2 2
( g)
Assume that C p,m is independent of temperature for all species in the reaction.
CH 3OH ( )
CH4 (g)
O2(g)
H !f
C p,m
(kJ/mol)
238.66
(Jmol1K1)
81.6
74.81
0
35.31
29.36
C p,m =
C
i
p,m
(i )
C p,m =
iC p,m (i )
= C p,m (CH 4 ) +
= 35.31 +
1
2
1
C
2 p,m
( 29.36)
(O 2 )
81.6 Jmol1K 1
$ 1 kJ '
= 313.47 kJ/mol + 31.61 Jmol1K 1 ( 773 298 K ) &
)
% 1000 J (
= 313.47 - 15.01 kJ/mol
17
11. Calculate the standard molar enthalpy change at 600 K for the reaction
N 2 ( g) + 3H 2 ( g) 2 NH 3 ( g) .
The standard molar enthalpies of formation and molar heat capacities at 25C are listed below. Assume
that the molar heat capacities are independent of temperature.
N2 (g)
H2 (g)
NH3 (g)
H !f
C p,m
(kJ/mol)
0
0
45.9
(Jmol1K1)
29.1
28.8
35.1
H R! = 2H !f ( NH 3 ) H !f ( N 2 ) 3H !f ( H 2 )
= 2 (45.9 kJ/mol) 0 3 ( 0 )
H R!
= 91.8kJ/mol.
C p,m = i C p,m (i )
i