CHAPTER 6

6.14 Consider these changes.

(a) Hg(l) Hg(g)
(b) 3O2(g) 2O3(g)
(c) CuSO4.H2O(s) CuSO4(s) + 5H2O(g)
(d) H2(g) + F2(g) 2HF(g)
At constant pressure, in which of the reactions is
work done by the system on the surroundings? By
the surroundings on the system? In which of them is
no work done?
•
6.14 Consider these changes.
(a) Hg(l) Hg(g)
(b) 3O2(g) 2O3(g)
(c) CuSO4.H2O(s) CuSO4(s) + 5H2O(g)
(d) H2(g) + F2(g) 2HF(g)
At constant pressure, in which of the reactions is
work done by the system on the surroundings? By
the surroundings on the system? In which of them is
no work done?
•
In (a) and (c), work is done by the system on the surroundings. In (b), work is done by the surroundings on the
system. In (d), no work is done.
6.15 A sample of nitrogen gas expands in volume
from 1.6 L to 5.4 L at constant temperature.
Calculate the work done in joules if the gas expands
(a) against a vacuum
(b) against a constant pressure of 0.80 atm,
(c) against a constant pressure of 3.7 atm.
 6.15
Recall that the work in gas expansion is equal to the product of the external, opposing pressure and the change in
volume.

(a) w PV

w (0)(5.4  1.6)L 0

(b) w PV

w (0.80 atm)(5.4  1.6)L  3.0 Latm

To convert the answer to joules, we write

101.3 J
w   3.0 L atm    3.0 102 J
1 L atm

(c) w PV

w (3.7 atm)(5.4  1.6)L  14 Latm

To convert the answer to joules, we write

101.3 J
w   14 L atm    1.4 103 J
1 L atm
6.19 Calculate the work done when 50.0 g of tin
dissolves in excess acid at 1.00 atm and 25C:
Assume ideal gas behavior
Sn(s) + (aq) (aq) + H2(g)
 6.19 Calculate the work done when 50.0 g of tin
dissolves in excess acid at 1.00 atm and 25C:
Assume ideal gas behavior
Sn(s) + (aq) (aq) + H2(g)
We first find the number of moles of hydrogen gas formed in the reaction:
1 mol Sn 1 mol H 2
50.0 g Sn    0.421 mol H 2
118.7 g Sn 1 mol Sn

The next step is to find the volume occupied by the hydrogen gas under the given conditions. This is the
change in volume.
nRT (0.421 mol)(0.0821 L atm / K mol)(298 K)
V    10.3 L H 2
P 1.00 atm

The pressure–volume work done is then:

101.3 J
w   PV   (1.00 atm)(10.3 L)   10.3 L atm    1.04 103 J
1 L atm
6.25 The first step in the industrial recovery of
copper from the copper sulfide ore is roasting, that is,
the conversion of CuS to CuO by heating:
2CuS(s) + 3O2(g) → 2CuO(s) + 2SO2(g)
ΔH: -805.6 kJ/mol
Calculate the heat evolved (in KJ) per gram of CuS
roasted.
 6.25 The first step in the industrial recovery of
copper from the copper sulfide ore is roasting, that is,
the conversion of CuS to CuO by heating:
2CuS(s) + 3O2(g) → 2CuO(s) + 2SO2(g)
ΔH: -805.6 kJ/mol
Calculate the heat evolved (in KJ) per gram of CuS
roasted.

The equation as written shows that 805.6 kJ of heat is released when two moles of CuS react. We want to calculate
the amount of heat released when 1 g of CuS reacts.

The heat evolved per gram of CuS roasted is

805.6 kJ 1 mol CuS
heat evolved =   4.213 kJ / g CuS
2 mol CuS 95.62 g CuS
6.27 Consider the reaction
2H2O(g) →2H2(g) + O2(g)
ΔH:483.6 kJ/mol
If 2.0 moles of H2O(g) are converted to H2(g) and
O2(g) against a pressure of 1.0 atm at 125C, what is
ΔU for this reaction?
 6.27 Consider the reaction
2H2O(g) →2H2(g) + O2(g)
ΔH:483.6 kJ/mol
If 2.0 moles of H2O(g) are converted to H2(g) and
O2(g) against a pressure of 1.0 atm at 125C, what is
E for this reaction?

We can calculate U using Equation (6.10) of the text.

UH − RTn

We initially have 2.0 moles of gas. Since our products are 2.0 moles of H 2 and 1.0 mole of O2, there is a
net gain of 1 mole of gas (2 reactants  3 products). Thus, n1. Looking at the equation given in the
problem, it requires 483.6 kJ to decompose 2.0 moles of water (H483.6 kJ). Substituting into the above
equation:
3
U483.6 10 J/mol − (8.314 J/molK)(398 K)(1)
5 2
U4.80 10 J/mol4.80 10 kJ/mol
6.33 A piece of silver of mass 362 g has a heat
capacity of 85.7 J/C. What is the specific heat of
silver?
6.33 A piece of silver of mass 362 g has a heat
capacity of 85.7 J/C. What is the specific heat of
silver?
6.37 A 0.1375-g sample of solid magnesium is
burned in a constant-volume bomb calorimeter that
has a heat capacity of 3024 J/C. The temperature
increases by 1.126C. Calculate the heat given off by
the burning Mg, in kJ/g and in kJ/mol.
 6.37 A 0.1375-g sample of solid magnesium is
burned in a constant-volume bomb calorimeter that
has a heat capacity of 3024 J/C. The temperature
increases by 1.126C. Calculate the heat given off by
the burning Mg, in kJ/g and in kJ/mol.
The heat gained by the calorimeter is
qCpt
3
q(3024 J/ C)(1.126 C) 3.405 10 J

The amount of heat given off by burning Mg in kJ/g is

1 kJ 1
(3.405 103 J)    24.76 kJ/g Mg
1000 J 0.1375 g Mg

The amount of heat given off by burning Mg in kJ/mol is

24.76 kJ 24.31 g Mg
  601.9 kJ/mol Mg
1 g Mg 1 mol Mg

If the reaction were endothermic, what would happen to the temperature of the calorimeter and the water?
6.38 A quantity of 2.00 x mL of 0.862 M HCl is mixed
with 2.00 x mL of 0.431 M Ba(OH)2 in a constant-
pressure calorimeter of negligible heat capacity. The
initial temperature of the HCl and Ba(OH)2 solutions is
the same at 20.48C. For the process

H(aq) + OH(aq) →H2O(l)

the heat of neutralization is 56.2 kJ/mol.

What is the final temperature of the mixed solution?
 qsolnqrxn0
the heat gained by the combined solution. How do we calculate the heat releas
qsoln qrxn  
we reacting 1 mole of H with 1 mole of OH ? How do we calculate the heat
6.38
solution?
First, let us set up how we would calculate the heat gained by the solution,
qqsoln msoln  tqrxn
Solution: Assuming no heat is lost to the surroundings, we can write:
soln
qsoln
ssoln
q 0
rxn
or m and s are the mass and specific heat of the solution and ttf ti.
where
qsoln qrxn
t, let us
We assume thatset up
the specific heathow we
of the solution is thewould calculate
same as the specific
First, let us set up how we would calculate the heat gained by the solution,
heat of water, an
that the density of the solution is the same as the density of water (1.00 g/mL). Since the de
g/mL, the mass of400
qsoln mLssoln
msoln of solution
t (200 mL  200 mL) is 400 g.
qsolnmsolnssolnt
where m and s are the mass and specific heat of the solution and ttf ti.
Substituting into the equation above, the heat gained by the solution can be represented as:
We assume that the specific
2 heat of the solution is the same as the specific hea
re m and s are the mass and specific h
q
that thesoln  (4.00 
density of the solutionJ/g
10 g)(4.184  C)(tsame
is the f 20.48 C) density of water (1.00 g/mL)
as the
g/mL, the mass of 400 mL of solution (200 mL  200 mL) is 400 g.
Next, let us calculate qrxn, the heat released when 200 mL of 0.862 M HCl is mixed with 20
Substituting into the equation above, the heat gained by the solution can be rep
0.431 M Ba(OH)2. The equation for the neutralization is
assumeq that (4.00 the
soln specific
10 g)(4.184
2 heat
J/g C)(t  20.48 C) of the so
f
2HCl(aq)  Ba(OH)2(aq)   2H2O(l)  BaCl2(aq)
theNext,
density
let us calculateof
q ,the
the heatsolution
rxn released when 200 is the
mL of 0.862 same
M HCl is m
Substituting into the equation above, the heat gained by the solution can be represented as:
2
qsoln(4.00 10 g)(4.184 J/g C)(tf 20.48 C)
6.38
Next, let us calculate qrxn, the heat released when 200 mL of 0.862 M HCl is mixed with 200 mL of
0.431 M Ba(OH)2. The equation for the neutralization is

2HCl(aq)  Ba(OH)2(aq)   2H2O(l)  BaCl2(aq)

There is exactly enough Ba(OH)2 to neutralize all the HCl. Note that 2 mole HCl  1 mole Ba(OH)2 and
that the concentration of HCl is double the concentration of Ba(OH)2. The number of moles of HCl is
0.862 mol HCl
(2.00 102 mL)   0.172 mol HCl
1000 mL

The amount of heat released when 1 mole of H is reacted is given in the problem ( 56.2 kJ/mol). The

amount of heat liberated when 0.172 mole of H is reacted is

 56.2 103 J
qrxn  0.172 mol    9.67 103 J
1 mol

Finally, knowing that the heat lost by the reaction equals the heat gained by the solution, we can solve for
the final temperature of the mixed solution.
Finally, knowing that the heat lost by the reaction equals the heat gained by the solution, w
6.38
the final temperature of the mixed solution.
qsoln qrxn
2 3
(4.00 10 g)(4.184 J/gC)(tf 20.48C)  ( 9.67 10 J)
3 4 3
(1.67 10 )tf (3.43 10 ) 9.67 10 J
tf26.3C
6.45 Which of the following standard enthalpy of
formation values is not zero at 25C? Na(s), Ne(g),
CH4(g), S8(s), Hg(l), H(g).
6.45 Which of the following standard enthalpy of
formation values is not zero at 25C? Na(s), Ne(g),
CH4(g), S8(s), Hg(l), H(g).

CH4(g) and H(g). All the other choices are elements in their most stable form ( H f  0 ). The most stable form
of hydrogen is H2(g).
6.51 Calculate the heat of decomposition for this
process at constant pressure and 25C:
CaCO3(s→CaO(s) + CO2(g)
(Look up the standard enthalpy of formation of the
reactant and products in Table 6.4.)
 6.51 Calculate the heat of decomposition for this
process at constant pressure and 25C:
CaCO3(s→CaO(s) + CO2(g)
(Look up the standard enthalpy of formation of the
reactant and products in Table 6.4.)

H   [H f (CaO)  H f (CO 2 )]  H f (CaCO3 )

H [(1)( 635.6 kJ/mol)  (1)( 393.5 kJ/mol)]  (1)( 1206.9 kJ/mol) 177.8 kJ/mol
6.52 The standard enthalpies of formation of ions in
aqueous solutions are obtained by a value of zero to
H ions; that is,
Δf [H(aq)] = 0.
(a)For the following reaction HCl(g) → (aq) + (aq)
(Δcalculate Δf for the Cl ions.
(b) Given that Δf for ions is 229.6 kJ/mol, calculate
the enthalpy of neutralization when
1 mole of a strong monoprotic acid (such as HCl) is
titrated by 1 mole of a strong base (such
as KOH) at 25C.
Solution: We use the H f values in Appendix 2 and Equation (6.18) of the text.

H rxn   nH f (products)   mH f (reactants)

 
(a) HCl(g)  H (aq)  Cl (aq)

H rxn  H f (H  )  H f (Cl  )  H f (HCl)

 74.9 kJ/mol 0  H f (Cl )  (1)( 92.3 kJ/mol)

H f (Cl  )   167.2 kJ/mol

(b) The neutralization reaction is

 
H (aq)  OH (aq)  H2O(l)
and,

H rxn  H f [H 2 O(l )]  [H f (H  )  H f (OH  )]

H f [H 2 O(l )]   285.8 kJ/mol (See Appendix 2 of the text.)


H rxn (1)( 285.8 kJ/mol)  [(1)(0 kJ/mol)  (1)( 229.6 kJ/mol)]  56.2 kJ/mol
6.57 From the standard enthalpies of formation,
calculate ΔH standard rxn for the reaction.
C6H12(l) + 9O2(g) →6CO2(g) + 6H2O(l)
For C6H12(l), Δf = -151.9 KJ/mol
 6.57 From the standard enthalpies of formation,
calculate ΔH standard rxn for the reaction.
C6H12(l) + 9O2(g) →6CO2(g) + 6H2O(l)
For C6H12(l), Δf = -151.9 KJ/mol
 6H f (CO2 )  6H f (H 2 O)  [Hf (C6 H12 )  9Hf (O2 )]

H (6)( 393.5 kJ/mol)  (6)( 285.8 kJ/mol)  (1)( 151.9 kJ/mol)  (l)(0)
 3924 kJ/mol

Why is the standard heat of formation of oxygen zero?

6.59 Determine the amount of heat (in kJ) given off
when 1.26 x g of ammonia are produced according to
the equation
N2(g) + 3H2(g) →2NH3(g)

ΔHrxn = -92.6 kJ/mol

Assume that the reaction takes place under standard
state condtions at 25 C.
 6.59 Determine the amount of heat (in kJ) given off
when 1.26 x g of ammonia are produced according to
the equation
N2(g) + 3H2(g) →2NH3(g)

ΔHrxn = -92.6 kJ/mol

Assume that the reaction takes place under standard
state condtions at 25 C.
4
This is an exothermic reaction. The amount of heat given off when 1.26 × 10 g of NH3 is produced is
1 mol NH3 92.6 kJ
(1.26 104 g NH3 )    3.43 104 kJ
17.03 g NH3 2 mol NH 3
6.61 From these data,
S(rhombic) + O2(g) →SO2(g) ΔH: -296.06 kJ/mol
S(monoclinic) + O2(g) → SO2(g) ΔH: -296.36
kJ/mol

calculate the enthalpy change for the transformation

S (rhombic) → S (monoclinic)
 6.61

S(rhombic) + O2(g) →SO2(g) ΔH: -296.06 kJ/mol

SO (g) → S(monoclinic) + O (g) ΔH: 296.36 kJ/mol
2 2

S(rhombic) → S(monoclinic) ΔH: 0.30 kJ/mol

6.69 Consider the reaction
N2(g) + 3H2(g) 2NH3(g)
Δ.6 KJ/mol

If 2.0 moles of N2 react with 6.0 moles of H2 to form

NH3, calculate the work done (in joules) against a
pressure of 1.0 atm at 25C. What is ΔU for this
reaction? Assume the reaction goes to completion.
 6.69 Consider the reaction
N2(g) + 3H2(g) 2NH3(g)
Δ.6 KJ/mol

If 2.0 moles of N2 react with 6.0 moles of H2 to form NH3, calculate the
work done (in joules) against a pressure of 1.0 atm at 25C. What is ΔU
for this reaction? Assume the reaction goes to completion.

6.69 We initially have 8 mole of gas (2 of nitrogen and 6 of hydrogen). Since our product is 4 mole of
ammonia, there is a net loss of 4 mole of gas (8 reactants  4 products). The corresponding volume loss
is
nRT (4.0 mol)(0.0821 L atm / K mol)(298 K)
V    98 L
P 1 atm

101.3 J
w   PV   (1 atm)( 98 L)  98 L atm   9.9 103 J  9.9 kJ
1 L atm

HUPV or UH PV

Using H as  185.2 kJ (2  92.6 kJ), (because the question involves the formation of 4 mole of
ammonia, not 2 mole of ammonia for which the standard enthalpy is given in the question), and  PV as
9.9 kJ (for which we just solved):
U 185.2 kJ  9.9 kJ  175.3 kJ
6.81 The combustion of what volume of ethane
(C2H6),measured at 23.0C and 752 mmHg, would be
required to heat 855 g of water from 25.0C to 98.0C?
6.81 The combustion of what volume of ethane (C2H6),measured at 23.0C and
752 mmHg, would be required to heat 855 g of water from 25.0C to 98.0C?
The combustion reaction is C2H6(l)  72 O2(g)   2CO2(g)  3H2O(l).

The heat released during the combustion of 1 mole of ethane is


H rxn  [2H f (CO2 )  3H f (H 2 O)]  [H f (C2 H 6 )  7 H  (O )]
2 f 2


H rxn [(2)( 393.5 kJ/mol)  (3)( 285.8 kJ/mol)]  [(1)( 84.7 kJ/mol  ( 72 )(0)]
 1559.7 kJ/mol

The heat required to raise the temperature of the water to 98 C is

5
q  mH 2O sH 2O t (855 g)(4.184 J/g C)(98.0  25.0) C 2.61 10 J 261 kJ

The combustion of 1 mole of ethane produces 1559.7 kJ; the number of moles required to produce 261 kJ

1 mol ethane
261 kJ   0.167 mol ethane
1559.7 kJ

The volume of ethane is

 L atm 
(0.167 mol)  0.0821 (296 K)
nRT  mol K 
Vethane  =  4.10 L
P  1 atm 
 752 mmHg  
 760 mmHg 
6.84 For which of the following reactions does ΔHorxn=
ΔHof ?

(a) H2(g) + S(rhombic) → H2S(g)

(b) C(diamond) + O2(g) → CO2(g)
(c) H2(g) + CuO(s) → H2O(l) + Cu(s)
(d) O(g) + O2(g) → O3(g)
6.84 Recall that the standard enthalpy of formation ( H f ) is defined as the heat change that results when 1
mole of a compound is formed from its elements at a pressure of 1 atm. Only in choice (a) does

H rxn  H f . In choice (b), C(diamond) is not the most stable form of elemental carbon under standard
conditions; C(graphite) is the most stable form.
6.96 (a) A person drinks four glasses of cold water
(3.0C) every day. The volume of each glass is 2.5 X102
mL. How much heat (in kJ) does the body have to
supply to raise the temperature of the water to 37C,
the body temperature? (b) How much heat would your
body lose if you were to ingest 8.0 x 102 g of snow at
0C to quench thirst? (The amount of heat necessary to
melt snow is 6.01 kJ/mol.)
 6.96
(a) The heat needed to raise the temperature of the water from 3 C to 37 C can be calculated using the
equation:
qmst

First, we need to calculate the mass of the water.

2.5 102 mL 1 g water

4 glasses of water    1.0 103 g water
1 glass 1 mL water

3
The heat needed to raise the temperature of 1.0 10 g of water is
3 5 2
qmst(1.0 10 g)(4.184 J/g C)(37  3) C 1.4 10 J 1.4 10 kJ

(b) We need to calculate both the heat needed to melt the snow and also the heat needed to heat liquid
water form 0 C to 37 C (normal body temperature).

The heat needed to melt the snow is

1 mol 6.01 kJ
(8.0 102 g)    2.7 102 kJ
18.02 g 1 mol
The heat needed to raise the temperature of the water from 0 C to 37 C is
2 5 2
qmst(8.0 10 g)(4.184 J/g C)(37  0) C 1.2 10 J 1.2 10 kJ

The total heat lost by your body is

2 2 2
(2.7 10 kJ)  (1.2 10 kJ) 3.9 10 kJ
6.98 Ice at 0C is placed in a Styrofoam cup containing
361 g of a soft drink at 23C. The specific heat of the
drink is about the same as that of water. Some ice
remains after the ice and soft drink reach an
equilibrium temperature of 0C. Determine the mass of
ice that has melted. Ignore the heat capacity of the
cup.(Hint: It takes 334 J to melt 1 g of ice at 0C.)
6.98 Heat gained by ice Heat lost by the soft drink
mice334 J/g  msdssdt
mice334 J/g  (361 g)(4.184 J/g C)(0  23) C
mice104 g