Solutions For Chemistry 4th CA Edition by Olmsted

SOLUTIONS MANUAL FOR CHEMISTRY 4TH CA
EDITION BY OLMSTED
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ISBN 9781119709411
Chemistry, 4e Instructor Solutions Manual Chapter 2
Chapter 2 The Behaviour of Gases
Solutions to Problems in Chapter 2

2.1 A pinhole in the top of the tube would let air leak into the space until the internal
pressure matched the external, atmospheric pressure. The barometer would then
indicate zero pressure, because the height of the mercury column is determined by the
pressure difference between inside and outside, and this difference would be zero in
the presence of a pinhole.
2.2 The arm of the manometer that feels the greater pressure will display the lower
height, so the right-hand side will be lower by 2 Δh.
2.3 When air is pumped into a flat tire, the tire expands and becomes hard. Both these
observations are the result of the pressure exerted by the gas molecules making up air.
2.4 The sail of a sailboat feels force from the wind, and this force causes the boat to move
across the water. Remember that pressure is defined to be force per unit area, so the
force of the wind demonstrates that the gas molecules making up air exert pressure
when they strike the sail.
2.5 Useful pressure conversion factors are 1 atm = 1.01325 × 105 Pa, 1 atm = 760 Torr,
and 1 bar = 105 pascals (Pa).
 1 atm   1.01325  10 Pa 
5
 = 6.07  10 Pa = 0.607 bar

4
(a) 455 Torr  
 760 Torr   1 atm 
 1.01325  105 Pa 
 = 2.48  10 Pa = 2.48 bar
5
(b) 2.45 atm 
 1 atm 
 1atm   1.01325  10 Pa 
5
−4
(c) 0.46 Torr    = 61 Pa = 6.1  10 bar
 760 atm  1 atm 
© 2021 John Wiley and Sons Canada, Ltd. 2-1

ISBN 9781119709411
 1.01325  105 Pa 
(d) 1.33  10−3 atm  −3
 =1.35  10 Pa =1.35  10 bar
2
 1 atm 
2.6 The SI unit for pressure is the pascal: 1 atm = 1.01325 × 105 Pa, and the atmosphere–
Torr conversion factor is 1 atm = 760 Torr.
 1 atm  760 Torr  −3
(a) 1.00 Pa    = 7.50  10 Torr
 1.01325  10 5
Pa  1 atm 
 105 Pa   1 atm  760 Torr 
 = 9.421  10 Torr
4
(b) 125.6 bar   
 1 bar  1.01325  10 5
Pa  1 atm 
 760 Torr 
 = 5.70  10 Torr
4
(c) 75.0 atm 
 1 atm 
 760 Torr 
(d) 4.55  10−10 atm  −7
 = 3.46  10 Torr
 1 atm 
2.7 The first part of this question asks about number of moles. Rearrange the ideal gas
equation to solve for n, and then substitute the appropriate values and do the
calculation:
pV (5.00 bar)(20.0 L)
n= = = 4.04 mol
RT (0.08314 L bar mol−1 K −1 )(298K)
The second part of the question asks about the volume if the pressure was different.
We can calculate this volume using n and the ideal gas equation, but we can also do
the calculation by using proportionalities.
pf Vf (5.00 bar)(20.0 L)
i i = pf Vf , from which Vi =
pV = = 100. L
pi 1.00 bar
2.8 The first part of this question asks about number of moles. Rearrange the ideal gas
equation to solve for n, and then substitute the appropriate values and do the
calculation:
pV (6.47 bar)(565 mL)(10−3 L/mL)
n= = = 0.149 mol
RT (0.08314 L bar mol−1 K −1 )(21.7 + 273.15 K)
The second part of the question asks about the volume if the pressure was different.
We can calculate this volume using n and the ideal gas equation, but we can also do
the calculation by using proportionalities.
(6.47 bar)(0.565 L)
i i = pf Vf , from which Vi =
pV = 3.62 L
(1.01 bar)
2.9 When some variables are held fixed, rearrange the ideal gas equation, pV = nRT, to

ISBN 9781119709411
collect fixed values on the right.
p nR p p
(a) n, R, V are constant: = = constant; i = f
T V Ti Tf
nRT
(b) V =
p
(c) n, R, T are constant: pV = nRT = constant; piVi = pfVf
2.10 To solve for one (or more) variables, rearrange the ideal gas equation, pV = nRT, to
collect the desired variable(s) on the left.
pV
(a) n =
RT
V RT Vi Vf
(b) p, R, T are constant: = = constant, giving =
n p ni nf
n p
(c) Divide both sides of the equation from (a) by V : =
V RT
2.11 When some conditions change but others remain fixed, rearrange the ideal gas
equation so the constant terms are grouped on the right. In this problem, n and p are
fixed:
V nR V V
= = constant, so i = f
T p Ti Tf
Vi = 0.255 L
Convert temperature to kelvins:
Ti = 25 + 273.15 = 298 K Tf = − 15 + 273.15 = 258 K

ViTf (0.255 L)(258 K)
Vf = = = 0.221 L
Ti (298 K)
2.12 When some conditions change but others remain fixed, rearrange the ideal gas
equation so the constant terms are grouped on the right. In this problem, n and V are
fixed:
p nR p p
= = constant, so i = f
T V Ti Tf
pi = 1.075 bar
Convert temperature to kelvins:

ISBN 9781119709411
Ti = 25 + 273.15 = 298 K
Tf = −15 + 273.15 = 258 K
piTf (1.075 bar)(258 K)
pf = = = 0.931 bar
Ti (298 K)
2.13 The equation is valid only for a gas for which n and T are fixed. (a) n and T are
fixed, so the equation is valid. (b) n can change, so the equation is not valid. (c) T
changes, so the equation is not valid. (d) The equation is not valid for liquids.
2.14 The equation is valid for a gas whose amount is fixed, provided T is in kelvins.
Thus, it could be used for (a) and (c) but not for (b) or (d).

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2.15 According to Dalton's law of partial pressures, each gas exerts a pressure equal to
the total pressure times its mole fraction. Mole fraction can be found from
concentration in ppm:
 ppm 
X= 6 
 10 
 0.78 molecules NO 2  -7
p NO2 = (1.011 bar)  6  = 7.9×10 bar
 10 molecules of air 
2.16 First convert ppm or % to a mole fraction, and then to a partial pressure. Remember
that standard atmospheric pressure is 1 atm:
 150 ppm  -4
X hydrocarbons =  6  = 1.5 × 10
 10 ppm 
 1.01325 bar 
p hydrocarbons = X hydrocarbons p total = (1.5 × 10-4 )(1atm)  -4
 = 1.52 ×10 bar
 1 atm 
 105 Pa 
p hydrocarbons = 1.52 × 10-4 bar   = 15.2 Pa
 bar 
 0.7 mol CO 
X CO =   = 0.007
 100 mol air 
 1.01325 bar 
p CO = X CO p total = (0.007)(1 atm)   = 0.00709 bar
 1 atm 
 105 Pa 
p CO = X CO p total = (0.00709 bar)   = 709 Pa
 bar 
2.17 According to Dalton’s law of partial pressures, each gas exerts a pressure equal to its
mole fraction times the total pressure: pi = Xiptotal. Standard atmospheric conditions
correspond to ptotal = 1 atm.
 101325 Pa 
pN2 = (0.7808)(1 atm)   = 79120 Pa
 1 atm 
 101325 Pa 
pO2 = (0.2095)(1 atm)   = 21230 Pa
 1 atm 
 101325 Pa 
pAr = (9.34 10−3 )(1 atm)   = 946 Pa
 1 atm 

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 101325 Pa 
pCO2 = (3.25  10−4 )(1 atm)   = 32.9 Pa
 1 atm 
2.18 To calculate partial pressures and mole fractions, first determine the number of
moles of each component of the gas mixture and then apply the ideal gas equation.
m n n RT
n= Xi = i pi = i
M ntotal V
 1 mol  −2
nAr = 1.25 g   = 3.13  10 mol
 39.95 g 
 1 mol  −2
nCO = 1.25 g   = 4.46  10 mol
 28.01 g 
 1 mol  −2
nCH4 = 1.25 g   = 7.79  10 mol
 16.04 g 
T = 375 + 273.15 = 648 K
Use the ideal gas equation to determine the partial pressures of each gas:
(3.13  10−2 mol)(0.08314 L bar mol−1 K −1 )(648 K)
pAr = = 0.422 bar
4.00 L
(4.46  10−2 mol)(0.08314 L bar mol−1 K −1 )(648 K)
pCO = = 0.601 bar
4.00 L
(7.79  10−2 mol)(0.08314 L bar mol−1 K −1 )(648 K)
pCH4 = = 1.05 bar
4.00 L
Obtain the total pressure from the sum of the partial pressures:
ptotal = 0.422 bar + 0.601 bar + 1.05 bar = 2.07 bar
Divide the moles of each component by the total number of moles:
ntotal = (3.13 + 4.46 + 7.79) × 10–2 mol = 1.538 × 10–1 mol
3.13  10−2 mol 4.46  10−2 mol
X Ar = = 0.204 X = = 0.290
1.538  10−1 mol 1.538  10−1 mol
CO
7.79  10−2 mol

X CH4 = = 0.507
1.538  10−1 mol
2.19 Molecular pictures show the relative numbers of molecules of various substances,
which also represent the relative numbers of moles of those substances. The figure
contains 8 He atoms and 4 O2 molecules.
(a) and (b) There are more He atoms, so the pressure due to He and the mole
fraction of He are higher.
nHe 8
(c) X He = = = 0.67
ntotal 12

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2.20 Molecular pictures show the relative numbers of particles of various substances,
which also represent the relative numbers of moles of those substances. Sample I
contains 4 A, 3 B, and 3 C, a total of 10 particles; Sample II contains 3 A, 6 B, and 7
C, a total of 16 particles; and Sample III contains 3 A, 5 B, and 18 C, a total of 26
particles.
(a) V and T are the same for all containers, so Sample I, which contains the largest
number of particles of A, has the highest value for pA.
(b) The mole fraction values for B are XI = 3/10 = 0.30, XII = 6/16 = 0.375, and XIII
= 5/26 = 0.192, so sample II has the highest value of XB.
(c) In Sample III, XA = 3/26 = 0.115; ppm = 106 X = 1.15 × 105 ppm.
2.21 To calculate partial pressures from a total pressure, mole fractions are required: pi =
Xi ptotal. Mole fractions can be calculated from the analytical data for the gas
sample. The equations needed to solve this problem are
m ni ni RT
n = Xi = pi =
M ntotal V
 1 mol  −2
nCH4 = 1.57 g   = 9.79  10 mol
 16.04 g 
 1 mol  −2
nC2H6 = 0.41 g   = 1.36  10 mol
 30.07 g 
 1 mol  −4
nC3H8 = 0.020 g   = 4.54  10 mol
 44.09 g 
ntotal = 9.79 × 10–2 mol + 1.36 × 10–2 mol + 4.54 × 10–4 mol = 1.120 × 10–1 mol.
Determine the mole fraction by dividing the moles of each component by the total
number of moles:
9.79  10−2 mol 1.36  10−2 mol

X CH4 = = 0.874 X C2 H 6 = = 0.121
1.120  10−1 mol 1.120  10−1 mol
4.54  10−4 mol
X C3H8 = = 4.06 10−3
1.120  10−1 mol
Multiply the mole fractions by the total pressure to obtain the partial pressure (round
the final values for ethane and propane to two significant figures, because their
masses are only known to two significant figures):

ISBN 9781119709411
pCH4 = (0.874)(2.35 bar) = 2.05 bar

pC2 H6 = (0.121)(2.35 bar) = 0.28 bar
pC3H8 = (4.06 10−3 )(2.35 bar) = 9.5  10−3 bar
2.22 To calculate partial pressures from a total pressure, mole fractions are required: pi =
Xi ptotal. Mole fractions can be calculated from the analytical data for the gas sample.
 ppm   ppb 
X = 6 = 9 
 10   10 
 10 Pa   487.4 molecules CO 2 
3
pCO2 = 113.1 kPa   6  = 55.12 Pa
 1 kPa   10 molecules of air 
 103 Pa   10.3 molecules NO  −3
pNO = 113.1 kPa   9  = 1.16 10 Pa
 1 kPa  10 molecules of air 
 103 Pa   4.2 molecules CO  −4
pCO = 113.1 kPa   9  = 4.8 10 Pa
 1 kPa   10 molecules of air 
2.23 Stoichiometric calculations require moles and a balanced chemical equation.

Balance the equation, determine the number of moles of CO2 produced, and apply
the ideal gas equation to calculate V:
The unbalanced chemical equation is
C6H12O6 + O2 → CO2 + H2O
6 C + 12 H + 8 O → 1 C + 2 H + 3 O
Give both CO2 and H2O a coefficient of 6 to balance C and H:
C6H12O6 + O2 → 6 CO2 + 6 H2O;
6 C + 12 H + 8 O → 6 C + 12 H + 18 O
This leaves 18 O on the product side. 6 O are from glucose, so O2 needs a coefficient
of 6 to balance O and obtain the balanced chemical equation:
C6H12O6 (g) + 6 O2 (g) → 6 CO2 (g) + 6 H2O (l)
Mglucose = 6(12.01 g/mol) + 12(1.01 g/mol) + 6(16.00 g/mol) = 180.18 g/mol. Use
mass–mole conversions to determine the moles of CO2 formed:
 1 mol   6 mol CO2  −1

nCO2 = 4.65 g C6 H12O6    = 1.548  10 mol
 180.18 g   1 mol C6 H12O6 

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nRT (1.548  10−1 mol)(8.314 L kPa mol −1 K −1 )(310 K)

V = = = 3.94 L
p 101.325 kPa
2.24 Stoichiometric calculations require moles and a balanced chemical equation.

Balance the equation, determine the moles of O2 produced, and apply the ideal gas
equation to calculate V.
The unbalanced equation is
KClO3 → KCl + O2
1 K + 1 Cl + 3 O → 1 K + 1 Cl + 2 O
Both K and Cl are already balanced. Balance O by giving O2 a coefficient of 3/2 and
then multiply all coefficients by 2 to eliminate fractions:
2 KClO3 → 2 KCl + 3 O2
M KClO3 = 39.10 g/mol + 35.45 g/mol + 3(16.00 g/mol) = 122.55 g/mol Use mass–
mole conversions to determine the moles of CO2 formed:
 1 mol   3 mol O 2  −2
nO2 = 1.57 g    = 1.92  10 mol
 122.55 g  2 mol KClO 3 
nRT  (1.92  10−2 mol)(0.08314 L bar mol −1 K −1 )(298 K) 

V= =  = 0.466 L
p  1.020 bar 
2.25 This is a stoichiometry problem that involves gases. We are asked to determine the
final pressure of the container (which is the pressure of chlorine gas). Begin by
analyzing the chemistry. The starting materials are Na metal and Cl2, a gas. The
product is NaCl. The balanced chemical reaction is 2 Na (s) + Cl2 (g) → 2 NaCl (s).
The problem gives information about the amounts of both starting materials, so this
is a limiting reactant situation. We must calculate the number of moles of each
species, construct a table of amounts, and use the results to determine the final
pressure. Calculations of initial amounts:
 1 mol 
nNa = 6.90 g   = 0.300 mol
 22.99 g 
For chlorine gas, use the ideal gas equation to do pressure–mole conversions. The
data must have the same units as those for R:
 1 bar 
pCl2 = 1.67  105 Pa  5  = 1.67 bar
 10 Pa 
pV (1.67 bar)(3.00 L)
nCl2 = = = 0.200 mol
RT (0.08314 L bar mol−1 K −1 )(300 K)
Divide each initial amount by its coefficient to determine the limiting reactant:

ISBN 9781119709411
0.300 mol
Cl2 : 0.200 mol Na: = 0. 150 mol (LR)
2
Use the initial amounts and the balanced equation to construct a table of amounts:
Reaction: 2 Na (s) + Cl2 (g) → 2 NaCl (s)

Initial amount (mol) 0.300 0.200 0.000
Change (mol) –0.300 –0.150 +0.300
Final amount (mol) 0.000 0.050 0.300
Use the final amount of Cl2 and the new temperature (47 °C) to calculate the pressure:
nRT (5.0  10−2 mol)(0.08314 L bar mol−1 K −1 )(320 K)

p= = = 0.443 bar
V 3.00 L
final partial pressure of each gas. Begin by analyzing the chemistry. The starting
materials are CO and O2, both gases. The product of the reaction is CO2.
The balanced chemical reaction is: 2 CO (g) + O2 (g) → 2 CO2 (g)
species, construct a table of amounts, and use the results to determine the partial
pressure. Use the ideal gas equation to determine the initial amounts of each gas:
p V (1.00 bar)(50.0 L)
nCO = CO = = 2.02 mol
RT (0.08314 L bar mol −1 K −1 )(298 K)
pO V (3.56 − 1.00 bar)(50.0 L)
nO2 = 2 = = 5.17 mol
RT (0.08314 L bar mol −1 K −1 )(298 K)
2.02 mol
O2 : 5.17 mol CO: = 1.01 mol (LR)
2
Use the initial amounts and the balanced equation to construct a table of amounts:
Reaction: 2 CO (g) + O2 (g) → 2 CO2 (g)
Initial amount (mol) 2.02 5.17 0.000
Change (mol) –2.02 –1.01 +2.02
Final amount (mol) 0.00 4.22 2.02
Obtain the partial pressures of each gas using the final amounts from the table:
pCO = 0
nRT (4.22 mol)(0.08314 L bar mol−1 K −1 )(298 K)
pO2 = = = 2.09 bar
V (50.0 L)
pCO2 = = = 1.00 bar
V (50.0 L)

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mass of product produced. Begin by analyzing the chemistry. The starting materials
are N2 and H2, both gases. The product of the reaction is NH3.
The balanced chemical reaction is N2 + 3 H2 → 2 NH3.
The problem gives information about the amounts of both starting materials, so this is
a limiting reactant situation. We must calculate the number of moles of each species,
construct a table of amounts, and use the results to determine the partial pressure. Use
the ideal gas equation to determine the initial amounts of each gas. The reactor
initially contains the gases in 1:1 mole ratio, so
275 bar
pi = = 137.5 bar for each gas
2
piV (137.5 bar)(8.75  103 L)

ni = = −1 −1
= 1.99  104 mol
RT (0.08314 L bar mol K )(455 + 273.15 K)
Since both gases have the same initial amount, the limiting reactant will be the one
with the larger stoichiometric coefficient: H2 is limiting. Here is the complete
amounts table:
Reaction: N2 (g) + 3 H2 (g) → 2 NH3 (g)

4
Initial amount (10 mol) 1.99 1.99 0.00
Change (104 mol) 1 –1.99 2
– (1.99) + (1.99)
3 3
Final amount (104 mol) 1.33 0.00 1.33
Obtain the mass of product formed from the final amount in the table:
 17.04 g 
mNH3 = nM = 1.33  104 mol   = 2.27  10 g
5
 1 mol 
mass of product produced. Begin by analyzing the chemistry.
The balanced chemical reaction is: 2 C2H4 (g) + O2 (g) → 2 C2H4O (g)
species, construct a table of amounts, and use the results to determine the partial
pressure. Use the ideal gas equation to determine the initial amounts of each gas.
The reactor initially contains the gases in 1:1 mole ratio, so

ISBN 9781119709411
1.00 bar
pi = = 0.500 bar for each gas
2
piV (0.500 bar)(5.00 10 4 L)
ni = = −1 −1
= 5.44  10 2 mol
RT (0.08314 L bar mol K )(280 + 273.15 K)
Since both gases have the same initial amount, the limiting reactant will be the one
with the higher stoichiometric coefficient: C2H4 is limiting. Here is the complete
amounts table:
Reaction: 2 C2H4 (g) + O2 (g) → 2 C2H4O (g)
Initial amount (102 mol) 5.44 5.44 0.00
2
Change (10 mol) –5.44 1 +5.44
− (5.44)
2
Final amount (102 mol) 0 2.72 5.44
Obtain the mass of product formed from the final amount in the table:
 44.05 g   10 kg 
−3
mC2H4O = nM = 5.44 102 mol    = 24.0 kg
 1 mol   1 g 
2.29 The yield in a reaction is the ratio of the actual amount produced to the theoretical
amount. The calculation in Problem 2.27 gives the theoretical amount:
 % yield 
Actual amount = theoretical amount  
 100% 
 13% 
Actual amount = 2.27  105 g   = 2.9  10 g
4
 100% 
2.30 The yield in a reaction is the ratio of the actual amount produced to the theoretical
amount. The calculation in Problem 2.28 gives the theoretical amount:
 % yield 
Actual amount = theoretical amount  
 100% 
 65% 
Actual amount = 24.0 kg   = 16 kg
 100% 
2Ekinetic
2.31 Molecular speed is related to temperature by the equations, v = , and
m
3RT 3RT
Ekinetic = , so v =
2N A mN A
. Thus, molecular speed increases with the square root of the absolute temperature, so
molecules will reach the detector sooner at higher temperature, because they have
greater speed.

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2.32 Molecular speed is related to temperature by the equations,

2 Ekinetic 3RT 3RT
v= , and Ekinetic = =, so v = . Thus, molecular speed varies as
m 2 NA mN A
the square root of the absolute temperature. At 200 K, the speeds will be smaller
200 K
than at 300 K by = 0.816. The easiest way to make a new drawing is to
300 K
duplicate Figure 2-10, changing the speed scale by this factor:
2Ekinetic
2.33 Molecular speed is related to temperature by two equations: v = ,
m
3RT 3RT
Ekinetic = , so v = . Each distribution of molecular speeds will have the
2N A mN A
T
same general shape, with the position of the peak depending on :
m

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2.34 Molecular speed is related to temperature by the equation,

2 Ekinetic 3RT 3RT
v= , and Ekinetic = =, so v = . Each distribution of molecular
m 2 NA mN A
speeds will have the same general shape, with the position of the peak depending on
T
:
m
2.35 Average molecular kinetic energy is directly proportional to temperature and is

3RT
independent of molecular mass: Ekinetic = . N2 and He at 300 K have identical
2N A
kinetic energy distributions, whereas the distribution for N2 at 200 K is shifted to
lower energy: The shape of the curve is slightly different for energies than for
speeds.

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2.36 Average molecular kinetic energy is directly proportional to temperature and is

3RT
independent of molecular mass: Ekinetic = . Br2 and Cl2 at 500 K have identical
2NA
kinetic energy distributions, whereas the distribution for Cl2 at 300 K is shifted to
lower energy: the shape of the curve is slightly different for energies than for
speeds.
2.37 The most probable speed at any temperature is related to the most probable kinetic
1 2Ekinetic, mp
energy by the equation Ekinetic = mv 2 , or vmp = . According to your
2 m
textbook, the most probable kinetic energy at 300 K is 4.13 × 10–21 J/molecule.
Because energy is proportional to temperature, the most probable kinetic energy at
Ekinetic, 2 T2
any other temperature can be calculated using proportions: = . Average
Ekinetic, 1 T1
kinetic energy, which is not the same as most probable kinetic energy because the
3
distribution of energies is asymmetric, is calculated using Ekinetic, molar = RT (T in
2
2 -2
kelvins; 1 J = 1 kg m s ):

ISBN 9781119709411
 4.00 g   10 kg  
−3
1 mol  −27
(a) He: m =     = 6.64  10 kg
 1 mol  1 g  6.022  10 23
atoms 
 900 K  −20
627 ºC + 273 = 900 K, Ekinetic, mp = 4.13 × 10–21 J   = 1.24  10 J
 300 K 
2(1.24  10−20 J)
vmp = −27
= 1.93  103 m/s
6.64  10 kg
Ekinetic, molar =
3
2
( 8.314 J mol−1 K −1 ) (900 K) = 1.12  104 J/mol
 32.00 g   10 kg  
−3
1 mol  −26
(b) O2: m =     = 5.31  10 kg
 1 mol  1 g  6.022  10 23
atoms 
27oC + 273 = 300 K, Ekinetic, mp = 4.13 × 10–21 J
2(4.13  10−21 J)
vmp = −26
= 3.94  102 m/s
5.31  10 kg
Ekinetic, molar =
3
2
(8.314 J mol−1 K −1 ) (300K) = 3.74  103 J/mol
(c) SF6: M = 32.066 g/mol + 6(18.998 g/mol) = 146.1 g/mol
 146.1 g   10 kg  
−3
1 mol  −25
m =    = 2.43  10 kg
 1 mol  1 g  6.022  10 23
atoms 
 900K  −20
627°C + 273 = 900 K, Ekinetic, mp = 4.13 × 10–21 J   = 1.24 10 J
 300K 
2(1.24  10−20 J)
vmp = −25
= 3.20  102 m/s
2.43  10 kg
Ekinetic, molar =
3
2
( 8.314 J mol−1 K −1 ) (900 K) = 1.12  104 J/mol
2.38 The most probable speed at any temperature is related to the most probable kinetic
1 2Ekinetic, mp
energy by the equation Ekinetic = mv 2 , or vmp = . According to your
2 m
ISBN 9781119709411
textbook, the most probable kinetic energy at 300 K is 4.13 × 10–21 J/molecule.
Because energy is proportional to temperature, the most probable kinetic energy at
Ekinetic, 2 T2
any other temperature can be calculated using proportions: = . Average
Ekinetic, 1 T1
kinetic energy, which is not the same as most probable kinetic energy because the
3RT
distribution of energies is asymmetric, is calculated using Ekinetic = per
2N A
3
molecule, or Ekinetic, molar = RT (T in kelvins; 1 J = 1 kg m 2 s −2 ):
2
 39.948 g   10 kg  
−3
1 mol  −26
(a) Ar: m =     = 6.63  10 kg
 1 mol  1 g  6.022  10 23
atoms 
 400 K 
127 °C + 273 = 400 K, Ekinetic, mp = 4.13 10 −21 J  −21
 = 5.51  10 J
 300 K 
2(5.51  10−21 J)
vmp = −26
= 4.08  102 m/s
6.63  10 kg
3
(
Ekinetic, molar =
2
8.314 J mol −1 K −1 ) ( 400 K ) = 4.99  103 J/mol
 131.29 g   10 kg  
−3
1 mol 
( )
b Xe : m =   
−25
 = 2.18  10 kg
 1 mol   1 g   6.022  10 atoms 
23
 400 K 
127 °C + 273 = 400 K, Ekinetic, mp = 4.13 10 −21 J  −21
 = 5.51  10 J
 300 K 
2(5.51  10−21 J)
vmp = −25
= 2.25  10 2 m/s
2.18  10 kg
3
(8.314 J mol−1 K −1 ) ( 400 K ) = 4.99  103 J/mol
Ekinetic, molar =
2
(c) C3 H8 : M = [3(12.01 g/mol) + 8(1.008 g/mol)] = 44.09 g/mol
 44.09 g   10 kg  
−3
1 mol  −26
m=    = 7.32  10 kg
 1 mol   1 g   6.022  10 molecules 
23
 600 K 
327 °C + 273 = 600 K, Ekinetic, mp = 4.13  10−21 J  −21
 = 8.26  10 J
 300 K 
2(8.26  10−21 J)
vmp = −26
= 4.75  10 2 m/s
7.32  10 kg
Ekinetic, molar =
3
2
(8.314 J mol−1 K −1 ) ( 400 K ) = 4.99  103 J/mol

ISBN 9781119709411
2.39 The ideal gas is defined by the conditions that molecular volumes and
intermolecular forces both are negligible.
(a) At very high pressure, molecules are very close together, so their volumes are
significant compared with the volume of their container; because the first condition
is not met, the gas is not ideal. Furthermore, intermolecular forces are significant
when the molecules are close together, which influences molecular motion.
(b) At very low temperature, molecules move very slowly, so the forces between
molecules, even though small, are sufficient to influence molecular motion; because
the second condition is not met, the gas is not ideal.

ISBN 9781119709411
2.40 Pressure is the effect of the impulses due to molecular collisions with the walls.
(a) Pushing the piston in compresses the gas, so the molecular density increases.
The frequency of molecular collisions with the walls increases, and so does the
pressure.
(b) Removing gas reduces the molecular density. Consequently, the frequency of
molecular collisions with the walls decreases, causing the pressure to decrease.
(c) Heating the gas increases the average molecular speed. Consequently, the force
exerted per collision and the frequency of collisions with the walls both increase,
causing the pressure to increase.
2.41 (a) If the piston is stationary and there is no friction, the forces and pressures on
each side must be equal, so the internal pressure is also 1 bar. This pressure is
generated by gas molecules colliding with the face of the piston.
(b) When temperature doubles, the increase in average molecular speed results in a
doubling of the pressure. The piston will move outward, causing the
concentration of gas molecules to decrease. This will lead to a lower frequency
of collisions with the wall, reducing the pressure. The piston will stop when the
internal pressure is once again 1 bar.
2.42 (a) For the same number of particles and unchanged temperature, the pressure will
nRT
be p = . At the molecular level, equal numbers of molecules impart an
V
equal set of impulses to the piston.
(b) When the external pressure is reduced, the piston moves out, reducing the
density of gas molecules and thereby reducing the rate of collisions with the face
of the piston.
2.43 As a gas cools, its molecules move more slowly, so they impart smaller impulses on
the walls of their container. This reduces the internal pressure, so the balloon

ISBN 9781119709411
collapses until the increase in gas density inside the balloon brings the internal
pressure back up to the external pressure of 1.000 bar.
2.44 As a gas cools, its molecules move more slowly, so they impart smaller impulses on
the walls of their container. This reduces the pressure exerted by the gas.
2.45 The ideal gas equation, pV = nRT, can be used to calculate moles using p–V–T data.
m
Molar mass is related to moles through n = :
M
pV m mRT
n= = M =
RT M pV
T = 25.0 + 273.15 = 298. K
Use the modified ideal gas equation to obtain the molar mass:
(2.55 g)(0.08314 L bar mol−1 K −1 )(298 K)

M= = 121 g/mol
(0.349 bar)(1.50 L)
The compound contains only C (12.0 g/mol), F (19.0 g/mol), and Cl (35.5 g/mol).
The formula can be determined by trial and error. The combination of 1 C, 2 F, and
2 Cl has
M = 1(12.0 g/mol) + 2(19.0 g/mol) + 2(35.5 g/mol) = 121 g/mol
This matches the experimental value. The formula is CF2Cl2.
2.46 The ideal gas equation, pV = nRT, can be used to calculate moles using p–V–T data.
m
Also, n = . These equations yield two expressions for n:
M
pV m mRT
n= = M=
RT M pV
Begin by converting the initial data into the units of R:
T = 21.5 + 273.15 = 294.7 K
 10−3 L 
V = 945 mL   = 0.945 L
 1 mL 
Use the modified ideal gas equation to obtain the molar mass:
(1.63 g)(0.08314 L bar mol −1 K −1 )(294.7 K)
M= = 28.1 g/mol
(1.50 bar)(0.945 L)
Knowing that the compound contains only C and H, find the formula by trial and

ISBN 9781119709411
error. There are 2 C = 24.02 g/mol, leaving 4 g/mol, which corresponds to 4 H. The
molecular formula is C2H4.
2.47 Density can be calculated from the ideal gas equation and mole–mass conversions:
m pV m pM
n = = =
M RT V RT
m pM (1.007 bar)(146.05 g/mol)

= = = 5.90 g/L
V RT (0.08314 L bar mol−1 K −1 )(27 + 273 K)
m pV m pM
n= = =
M RT V RT
m pM (0.507 bar)(2.016 g/mol)
= = −1 −1
= 4.91  10−2 g/L
V RT (0.08314 L bar mol K )( −23 + 273 K)
2.49 Molecular speed can be calculated from temperature and molar mass:
3RT 1
Ekinetic = Ekinetic = 2
mv rms
2N A 2
1/ 2
2 3RT 3RT  3RT 
v = = v =  
mN A M  M 
T = 27 °C + 273 = 300. K; M = 32.06 g/mol + 6(18.998 g/mol) = 146.0 g/mol. The

mass must be converted to kg/mol for mass units to cancel (1 J = 1 kg m2 s–2): M =
(146.0 g/mol)(10–3 kg/g) = 1.460 × 10–1 kg/mol
1/2
 3(8.314 J mol−1 K −1 )(1 kg m 2s −2 /J)(300. K) 
vrms =  = 226 m/s
 1.460  10−1 kg/mol 

ISBN 9781119709411
2.50 Molecular speed can be calculated from temperature and molar mass:
3RT 1
Ekinetic = Ekinetic = mvrms
2
2NA 2
1/2
3RT 3RT  3RT 
v2 = = v = 
mN A M  M 
T = −23 °C + 273 = 250. K; M = 2(1.0078 g/mol) = 2.0156 g/mol
The mass must be converted to kg/mol for mass units to cancel (1 J = 1 kg m 2 s −2 ):
M = (2.0156 g/mol)(10−3 kg/g) = 2.0156  10−3 kg/mol
1/2
 3(8.314 J mol−1 K −1 )(1 kg m 2s −2 /J)(250. K) 
v =  = 1.76  103 m/s
 2.0156  10−3 kg/mol 
2.51 Rates of diffusion and effusion depend on the molar masses of the gases because
average speeds determine these rates, and these are given by Equation 2-5:
1/2
 3RT 
vrms =   . For two gases at the same temperature, the one with the smaller
 M 
molar mass has the faster molecular speed and will diffuse faster. Thus, CH4 (M =
16 g/mol) diffuses faster through the atmosphere than C2H6 (M = 30 g/mol).
2.52 Rates of diffusion and effusion depend on the molar masses of the gases because
average speeds determine these rates, and these are given by Equation 2-5:
1/2
 3RT 
vrms =   . For two gases at the same temperature, the one with the smaller
 M 
molar mass has the faster molecular speed and will effuse faster. The molar masses
of CO and N2 are the same, however (M = 28 g/mol), so the average molecular
speeds of these two gases are the same and they could not be separated by effusion.
effusion rateA MB
2.53 = (by Graham's Law)
effusion rateB MA

ISBN 9781119709411
M 14 CO = 14 + 2(16) = 46 g / mol
2
M 12 CO = 12 + 2(16) = 44 g / mol
2
effusion rate 14 CO 44 g / mol

thus, 2
= = 0.98
2
M 14 CO = 14 + 16 = 30 g / mol
M 12 CO = 12 + 16 = 28 g / mol
thus, = = 0.97
It should be easier to separate 14C from 12C in the form of the monoxide rather than
the dioxide, but the values are very close.
2.54 After one diffusion step, the concentration of 235UF6 will be 1.0043(0.71%) =
0.713%, after two steps it will be 1.0043(0.713%) = 0.716%, etc. In general, the %
of 235UF6 after n diffusion steps will therefore be 0.71%(1.0043)n.
After 100 steps, %235UF6 = 0.71%(1.0043)100 = 1.09%
After 500 steps, %235UF6 = 0.71%(1.0043)500 = 6.07%
2.55 Ideal pressure for F2 (g):
nRT (1.00 mol)(0.08314 L bar K −1 mol−1 )(298K)

p= = = 0.826 bar
V 30.0 L
Real pressure for F2 (g):
2
nRT n
p= − a 
V − nb V 
2
(1.00 mol)(0.08314 L bar K −1 mol−1 )(298 K)  1.00 mol 
= − (1.171 bar L2 mol− 2 )  
30.0 L − (1.00 mol)(0.0290 L / mol)  30.0 L 
= 0.827 bar − 0.0013 bar
= 0.826 bar
The two values are similar because the pressure is low enough that the molecules
are far apart and intermolecular forces are small. Also, the temperature is high
enough that the kinetic energy of the molecules is high enough to overcome what
intermolecular forces do exist.
2.56 Ideal pressure for F2 (g):

ISBN 9781119709411
nRT (100 mol) (0.08314 L bar K −1 mol−1 )(298K)

p= = = 82.6 bar
V 30.0 L
Real pressure for F2 (g):

2
nRT n
p= − a 
V − nb V 
2
(100 mol)(0.08314 L bar K −1 mol −1 )(298 K)  100 mol 
= − (1.171 bar L2 mol −2 )  
30.0 L − (100 mol)(0.0290 L / mol)  30.0 L 
= 91.42 bar − 13.01 bar
= 78.4 bar
The real pressure is lower than the ideal pressure because of strong intermolecular
forces among F2 molecules at this high pressure.
2.57 Real pressure of H2 (g):
2
nRT n
p= − a 
V − nb V 
2
(100 mol)(0.08314 L bar K −1 mol−1 )(298 K)  100 mol 
= − (0.247 bar L2 mol− 2 )  
30.0 L − (100 mol)(0.0266 L / mol)  30.0 L 
= 90.62 bar − 2.74 bar
= 87.9 bar
This value is higher than that calculated for fluorine in the previous problem
because the intermolecular forces in hydrogen are smaller, because hydrogen is a
much smaller molecule than fluorine.
2.58 The van der Waals a term for chlorine is much larger than that of fluorine.
Likewise, the van der Waals b term for chlorine is much larger than that of fluorine.
According to the van der Waals equation, a larger a term will result in a lower
pressure, but a larger b term will result in a higher pressure. However, the a term
has a larger effect on pressure than does the b term. Chlorine will therefore have a
lower pressure than fluorine under the same conditions.
2.59 Real pressure of O2 (g):

ISBN 9781119709411
2
nRT n
p= − a 
V − nb V 
2
(75 mol)(0.08314 L bar K −1 mol −1 )(298 K)  75 mol 
= − (1.378 bar L2 mol − 2 )  
15.0 L − (75 mol)(0.0318 L / mol)  15.0 L 
= 147.3 bar − 34.5 bar
= 112.8 bar
2.60 The pressure at 700 oC can be calculated using the van der Waals equation:
2
nRT n
p= − a 
V − nb V 
2
(75 mol)(0.08314 L bar K −1 mol −1 )(700 + 273 K)  75 mol 
= − (1.378 bar L2 mol− 2 )  
15.0 L − (75 mol)(0.0318 L / mol)  15.0 L 
= 480.95 bar − 34.45 bar
= 446 bar
This is greater than the maximum pressure for this cylinder, so an explosion is
likely.
2.61 Use the ideal gas equation to determine moles, and then do mole–mass–number
conversions:
pV  (10.0 bar)(725 mL)   10−3 L  −2

n= =   = 7.28  10 mol
RT  (0.08314 L bar mol−1 K −1 )(925 + 273 K)   1 mL 
m = nM = (7.28  10−2 mol)(83.80 g/mol) = 6.10 g
# atoms = nN A = (7.28  10−2 mol)(6.022  1023 atoms/mol)= 4.38  1022 atoms
2.62 Use the ideal gas equation to determine moles, and then do mole–mass conversions:
pV (145 bar)(9.50 L)
n= = = 55.6 mol
RT (0.08314 L bar mol−1 K −1 )(298 K)
m = nM = (55.6 mol)(28.02 g/mol) = 1.56 103 g
which also represent the relative numbers of moles of those substances. Chamber A
contains 6 atoms, B contains 12 atoms, and C contains 9 atoms, for a total of 27
atoms, and the chambers have equal volumes and are at the same temperature.
(a) Chamber B contains the most atoms, so it exhibits the highest pressure.
(b) The pressures in the chambers are proportional to the number of atoms:

ISBN 9781119709411
#  6
pA = pB  A  = 1.0 bar   = 0.50 bar
 #B   12 
(c) The pressure will increase in proportion to the number of atoms:
#   27 
pnew = pold  new  = 1.0 bar   = 4.5 bar
 #old   6 
(d) When the valves are opened, the number of atoms in each chamber equalizes:
27
=9
3
#  9
pnew = pold  new  = 0.50 bar   = 0.38 bar
 #old   12 
which also represent the relative numbers of moles of those substances. Tank 1, with
a volume of 40 L, contains 10 atoms; tank 2, with a volume of 10 L, also contains 10
atoms.
(a) When the valve is opened, the pressures in the two tanks equalize, and the
molecules are distributed in proportion to the volumes. Tank 1 contains four times as
many molecules as tank 2, because its volume is four times as large. Thus, tank 1
contains eight molecules of each kind, and tank 2 contains two of each kind:
nRT (20 mol)(0.08314 L bar mol −1 K −1 )(0 + 273 K)

(b) p = = = 9.1 bar
V (40 L + 10 L)
ni RT (10 mol)(0.08314 L bar mol −1 K −1 )(0 + 273 K)
(c) pi = = = 23 bar
V (10 L)
The total pressure will therefore be 2(23 bar) = 46 bar
2.65 Much of the information in this problem is not needed, because molecular speed can
be calculated from temperature and molar mass:

ISBN 9781119709411
3RT 1
Ekinetic = Ekinetic = mv 2
2NA 2
1/2
2 3RT 3RT  3RT 
v = = v=  
mN A M  M 
The mass must be converted to kg/mol for mass units to cancel (1 J = 1 kg m2 s–2):
 16.00 g   1 kg  −3
M = 3   = 48.00  10 kg/mol
 1 mol   1000 g 
1/2
 3(8.314 J mol −1 K −1 )( − 25 + 273 K) 
v=  = 359 m/s
 48.00  10−3 kg/mol 
2.66 To calculate the pressure, we need the temperature, which can be found from the
3RT
average kinetic energy: Ekinetic = ;
2N A
2N A Ekinetic 2(6.022  1023 mol−1 )(1.02  10−20 J)
T= = = 493 K
3R 3(8.314 J mol−1 K −1 )
m 1.55 g
n= = = 3.88  10−2 mol
M 39.95 g/mol
nRT (3.88  10−2 mol)(0.08314 L bar mol−1 K −1 )(493 K)
p= = = 0.318 bar
V 5.00 L
The average speed can be calculated either from the average kinetic energy or from
1/2
 3RT 
the temperature: v =   .
 M 
The molar mass must be converted to kg/mol for mass units to cancel: M = 39.95
g/mol or 39.95 × 10–3 kg/mol
3(8.314 J mol−1 K −1 )(493 K)(1 kg m 2s −2 /J)
1/2
 3RT 
v=  = −3
= 5.55  102 m/s
 M  39.95  10 kg/mol
2.67 Use the ideal gas equation to find molar density and Avogadro’s number to convert
to molecular density:
n p 10−10 bar
= = −1 −1
= 4  10−12 mol/L
V RT (0.08314 L bar mol K )(310 K)
 n   6.022  10 molecules  4  10 mol 

23 −12
#
= NA   =    = 2  10 molecules/L
12
V   
V 1 mol  1 L 

ISBN 9781119709411
2.68 Use Avogadro’s number to convert to a molar density and the ideal gas equation to
calculate p:
3
n  1010 molecules   1 mol   10 m 
−2
 103 cm 3 
=     
1 m3   6.022  10 molecules   1 cm 
23
V   1L 
= 1.7  10−17 mol/L
n
p = RT = (0.08314 L bar mol −1 K −1 )(25 K)(1.7 10 −17 mol/L) = 4  10−17 bar
V
(There is one significant figure because molecular density is known to only one
significant figure.)
2.69 The molar mass of gaseous oxygen can be determined using the ideal gas law:
mRT
M =
pV
Pump out a bulb of known volume, weigh the empty bulb, fill the bulb with oxygen
at a measured pressure, and weigh again. For monatomic oxygen, this experiment
would give M = 16.00 g/mol, whereas it would give M = 32.00 g/mol for the
diatomic gas.
2.70 Molar mass can be determined using the ideal gas equation and the relationship
mRT
between mass and moles: M = . Thus, the experiment must include
pV
measurements of the mass, temperature, pressure, and volume of the gas sample
whose molar mass is to be calculated. Weigh an evacuated gas bulb. Determine the
volume of the bulb by filling it with water and weighing it again. Empty, dry, and
pump out the bulb, and then fill it with SO2 gas to a measured pressure. Weigh again
to determine m, from which the molar mass of the gas can be determined. If there is
a significant amount of S2O4 present, the molar mass will be greater than 64 g/mol,
the molar mass of pure SO2.
2.71 Use Dalton’s law of partial pressures to determine partial pressures, and then apply
the ideal gas equation to calculate masses.

ISBN 9781119709411
1.00
X C3H6 = = 0.200 pC3H6 = 0.200 bar
5.00
X O2 = 1.000 − 0.200 = 0.800 pO2 = 0.800 bar
pVM (0.200 bar)(2.00 L)(42.078 g/mol)
mC3H6 = = = 0.682 g
RT (0.08314 L bar mol−1 K −1 )(23.5 + 273.15 K)
pVM (0.800 bar)(2.00 L)(32.00 g/mol)
mO2 = = = 2.08 g
RT (0.08314 L bar mol−1 K −1 )(23.5 + 273.15 K)
2.72 First calculate moles of each gas, and then apply the ideal gas equation.
 1 mol  −2
nAr = 1.00 g   = 2.50  10 mol
 39.95 g 
 1 mol  −3
nNe = 0.0500 g   = 2.48  10 mol
 20.18 g 
2.50  10−2 mol
X Ar = = 0.910
(2.50  10 −2 mol) + (2.48  10 −3 mol)
2.48  10−3 mol
X Ne = = 0.0902
(2.50  10 −2 mol) + (2.48  10 −3 mol)
nRT (2.75  10 −2 mol)(0.08314 L bar mol −1 K −1 )(275 K)
ptotal = = = 0.126 bar
V 5.00 L
pAr = (0.910)(0.126 bar) = 0.114 bar
pNe = (0.0902)(0.126 bar) = 0.0114 bar
2.73 All conditions except the volumes are different for the two samples.
(a) The bulb with the larger number of moles will contain more molecules:
pV (2 bar)V V 
nH 2 = = = 7  10 −3   mol
RT (273 K)R R
pV (1 bar)V V 
nO2 = = = 3  10 −3   mol
RT (298 K)R R
The bulb of hydrogen contains more molecules.
V   2.01 g  −2  V 
(b) mH2 = (7  10 −3 )   mol   = 1  10   g
R  1 mol  R
V   32.00 g  −1  V 
mO2 = (3  10 −3 )   mol   = 1  10   g
R  1 mol  R
The bulb of oxygen contains more mass.

ISBN 9781119709411
(c) The average kinetic energy of molecules depends only on the temperature of the
gas, so the oxygen molecules, being at higher temperature, have greater average
kinetic energy.
T 3RT
(d) The average molecular speed depends on because v = . The
m mN A
 273 
temperature ratio of H 2 :O2 is   = 0.916 , whereas the mass ratio is
 298 
 2  T 0.916
  = 0.0625 Thus, = = 3.83 , so the hydrogen molecules have
 32  m 0.0625
greater average speed by this factor.
2.74 (a) Since we know that both bulbs have the same volume,
nCl2 pCl2 TN2 2 bar(298 K)
= = = 1.6. Therefore, there are 1.6 moles of Cl2 per mole
nN2 pN2 TCl2 1 bar(373 K)
of N2, so there are also more molecules of Cl2.
(b) To determine mass, we must multiply moles by molar mass. Since there are a
greater number of moles of Cl2 gas and Cl2 has the higher molar mass, it is easy
to see that the Cl2 bulb has more mass.
3RT
(c) Using the equation: Ekinetic = , the bulb at the higher temperature will have
2N A
the higher kinetic energy. Again, this bulb is the Cl2 bulb at 100 ºC compared
with the nitrogen bulb at 25 ºC.
1/2
 3RT 
(d) Using the equation v =   we can determine the average molecular speed
 M 
for each bulb: 1 kg m 2s −2 /J
 1 mol  −2
nAr = 1.00 g   = 2.50  10 mol
 39.95 g 
 1 mol  −3
nNe = 0.0500 g   = 2.48  10 mol
 20.18 g 
2.50  10−2 mol
X Ar = = 0.910
(2.50  10 −2 mol) + (2.48  10 −3 mol)
2.48  10−3 mol
X Ne = = 0.0902
(2.50  10 −2 mol) + (2.48  10 −3 mol)
nRT (2.75  10 −2 mol)(0.08314 L bar mol −1 K −1 )(275 K)
ptotal = = = 0.126 bar
V 5.00 L
pAr = (0.910)(0.126 bar) = 0.114 bar
pNe = (0.0902)(0.126 bar) = 0.0114 bar

ISBN 9781119709411
3(8.314 J mol −1 K −1 )(373 K)(1 kg m 2s −2 /J)

Cl2 : v = = 362 m/s
70.90 10−3 kg/mol
3(8.314 J mol −1 K −1 )(298 K)(1 kg m 2s −2 /J)
N2: v = = 515 m/s
28.02  10 −3 kg/mol
Therefore, the N 2 bulb has a higher average molecular speed.
2.75 (a) The most probable kinetic energy at 300 K is 4 × 10–21 J.
m(vmost probable )2
(b) Ekinetic (most probable) = (Remember 1 J = 1 kg m 2 s −2 )
2
2(4  10−21 J)(6.022  1023 molecules/mol)

vmost probable = = 4  102 m/s
32.00  10−3 kg/mol
2.76 (a) The most probable speed is the speed possessed by the largest number of
molecules. Reading from the graph, this is 8 × 102 m/s (the peak position cannot
be determined to better than one significant figure).
1
(b) Ekinetic = mv2; because 1 J = 1 kg m2 s–2, molecular mass must be expressed in
2
kg:
  10 kg 
−3
M  17.03 g/mol −26
m= =   = 2.83  10 kg
N A  6.022  10 molecules/mol   1 g 
23
1
Ekinetic = (2.83  10 −26 kg)(8  10 2 m/s) 2 = 9  10 −21 kg m 2 s −2 = 9  10−21 J
2
2.77 Each part of this problem represents a change of one or more conditions, for which a
rearranged version of the ideal gas law can be used.
pV
(a) T and n are fixed, so pV = nRT = constant and Vf = i i
pf
(0.700 bar)(3.00 L)
Vf = = 2.09 L
1.007 bar
pV
(b) T and n are fixed, so pV = nRT = constant and pf = i i
Vf
(0.700 bar)(3.00 L)
pf = = 1.05 bar
2.00 L

ISBN 9781119709411
p pT
(c) V and n are fixed, so = constant and pf = i f
T Ti
(0.700 bar)(50.0 + 273.15 K)

pf = = 0.828 bar
273.15 K
2.78 Each part of this problem represents a change of one or more conditions, for which a
rearranged version of the ideal gas law can be used.
pV
(a) T and n are fixed, so pV = nRT = constant and Vf = i i
pf
(0.429 bar)(2.00 L)
Vf = = 1.23 L
0.700 bar
(b) Here, pressure, temperature, and volume are changing. So the rearranged ideal
pVT
gas law is pf = i i f
Vf Ti
(0.429 bar)(2.00 L)(50.0 + 273.15 K)
Pf = = 0.495 bar
(1.50 L)(100.00 + 273.15 K)
(c) Here, only pressure and number of moles are changing. So the ideal gas law can
pn
be rearranged to pf = i f
ni
(0.429 bar)(1 mol)
pf = = 0.215 bar
2 mol
2.79The figure illustrates atomic density and atomic motion of a sample of helium gas.
The figure contains eight atoms:
(a) Your drawing should show the same atomic density as the original figure but with
longer “tails” on the atoms, indicating that they are moving at higher speeds:
(b) Your drawing should show the same lengths of “tails” as in the original figure,
but there should be two fewer atoms:

ISBN 9781119709411
(c) Your drawing should be the same as the original figure except that half the atoms
should be replaced with diatomic molecules:
2.80 The figure illustrates atomic density and atomic motion of a sample of helium gas.
The figure contains eight atoms:
(a) Your drawing should show the same lengths of “tails” as in the original figure
(the speed of the molecules is not changing), but there should be half as many
atoms.
(b) Your drawing should be the same as the original figure except that all the helium

ISBN 9781119709411
atoms are replaced with nitrogen molecules.
(c) Your drawing should be the same as the original figure except the tails should be
shorter on the atoms.
2.81 Use the ideal gas equation, pV = nRT, to determine which statements are correct:
p RT
(a) At constant T and V, = = constant. Thus, p is directly proportional to
n V
number of moles of gas. The statement is false.
p nR p
(b) At constant V and n, = = constant ; is constant. The statement is true.
T V T
p nR p
(c) At fixed V and n, = = constant ; is constant; pT is not. The statement is
T V T
false.
2.82 Use the ideal gas equation, pV = nRT, to determine which statements are correct:
V nR
(a) False. At fixed n and p, = = constant. Thus, V is directly proportional to T.
T p
(b) At fixed n and T, pV = nRT = constant. The statement is true.
p RT
(c) False. At fixed V and T, = = constant. Thus, the pressure increases as n
n V
increases.
2.83 This is an application of the ideal gas equation to changing gas conditions. The only

ISBN 9781119709411
pV pV pV
constant quantity is n, so = nR = constant. Therefore, i i = f f .
T Ti Tf
pi = 0.969 bar Vi = 0.963 L pf = 1.00 bar

Ti = 22 + 273.15 = 295 K Tf = 15 + 273.15 = 288 K
 pV  T  (0.969 bar)(0.963 L)(288 K)
Vf =  i i   f = = 0.911 L
 Ti   pf  (295 K)(1.00 bar)
2.84 There is enough information given to calculate p directly from the ideal gas
equation.
m 96.0 g
n= = = 3.00 mol
M 32.00 g/mol
V = 3.00 L T = 27 + 273 = 300. K
nRT  (3.00 mol)(0.08314 L bar mol−1 K −1 )(300. K) 
p= =  = 29.4 bar
V  3.00 L 
2.85 Concentrations in parts per billion can be converted to mole fractions, and the partial
pressure can then be calculated using pi = Xiptotal. To determine molecular
concentration, first use the ideal gas equation to calculate n in moles, and then
N
multiply by A :
V
X SF6 = (1.0 ppb)(10 −9 /ppb) = 1.0  10 −9 pSF6 = (1.0  10 −9 )(1 bar) = 1.0  10 −9 bar
 10−3 L 
V = 1.0 cm 3  3 
= 1.0  10 −3 L
 1 cm 
pV (1.0  10 −9 bar)(1.0  10 −3 L)
n= = −1 −1
= 4.1  10 −14 mol
RT (0.08314 L bar mol K )(21 + 273.15 K)
# (4.1  10 −14 mol)(6.022  10 23 molecules/mol)
= = 2.5  1010 molecules/L
V 1L
2.86 Concentrations in parts per million can be converted to mole fractions, and the
partial pressure can then be calculated using pi = Xiptotal. To determine molecular
concentration, first use the ideal gas equation to calculate mol/L, and then multiply
by NA:

ISBN 9781119709411
X CO2 = (385 ppm)(10−6 /ppm) = 3.85  10 −4

pCO2 = (3.85  10−4 )(1 bar) = 3.85  10 −4 bar
n p 3.85  10−4 bar
= = −1 −1
= 2.03  10−5 mol/L
V RT (0.08314 L bar mol K )( − 45 + 273.15 K)
#  6.022  1023 molecules   2.03  10−5 mol 
=   = 1.2  10 molecules/L
19
V  1 mol  1.0 L 
2.87 This is a P–V–T problem. First calculate moles of CO2, and then use the ideal gas
equation to calculate the final pressure:
m 15.00 g
n = = = 0.3408 mol
M 44.01 g/mol
(0.3408 mol)(0.08314 L bar mol −1 K −1 )(273.15 K)
pCO2 = = 10.3 bar
0.750 L
2.88 (a) To determine the number of moles of each gas, we only need the information of
the individual containers. Moles can be calculated by direct application of the
ideal gas equation:
pV (2.0 bar)(15 L)
nN2 = = = 1.2 mol
RT (0.08314 L bar mol −1 K −1 )(300. K)
pV (3.0 bar)(1.5 L)
nO2 = = = 0.18 mol
RT (0.08314 L bar mol −1 K −1 )(300. K)
(b) Remember that the pressure of one gas will not affect the pressure of the other.
Therefore, treat the expansion as a change of volume at constant n and T, so pV
= constant, thus pfVf = piVi
p V (2.0 bar)(15 L)
pf, N 2 = i i = = 1.8 bar
Vf (15 + 1.5 L)
piVi (3.0 bar)(1.5 L)
pf, O2 = = = 0.27 bar
Vf (15 + 1.5 L)
(c) The oxygen molecules will be distributed evenly throughout the volume, so the
fraction in the smaller chamber will be the fraction of that chamber’s volume
V 1.5 L 1
relative to the total volume. small = = = 0.091. There will be
Vtotal 1.5 L + 15 L 11
1/11 of the molecules in the smaller container.

ISBN 9781119709411
m pV m pM
n= = , from which =
M RT V RT
First, calculate the average molar masses of dry air and of moist air:
Mair = Σi(XiMi)
Mdry air = (0.7808)(28.01 g/mol) + (0.2095)(32.00 g/mol) + (9.34 × 10–3)(39.948

g/mol) = 28.95 g/mol
For moist air at 298 K:
 1 bar  −2
pH2O = 3167 Pa  5  = 3.17  10 bar X H2O = 0.0317
 10 Pa 
The total mole fraction of the dry air components is reduced from 1 to (1 – .0317) =
0.9683. Each dry air mole fraction must be multiplied by this factor to obtain the
mole fractions in moist air. Thus,
Mmoist air = (0.0317)(18.01 g/mol) + (0.9683)(28.95 g/mol) = 28.60 g/mol
m (1 bar)(28.95 g/mol)

  = = 1.17 g/L
 V dry air (0.08314 L bar mol −1 K −1 )(298 K)
m (1 bar)(28.60 g/mol)
  = = 1.15 g/L
 V  moist air (0.08314 L bar mol −1 K −1 )(298 K)
2.90 The concentration in parts per million can be converted to a mole fraction, and the
partial pressure can then be calculated using pi = Xiptotal. To determine molecular
concentration, first use the ideal gas equation to calculate mol/L, and then multiply
by NA:
0.50 molecules of O3
X O3 = 6 = 5.0 10−7
10 molecules of air
pO3 = (5.0 10−7 )(1.016 bar) = 5.1  10−7 bar
n p 5.1  10−7 bar
= = = 2.0  10−8 mol/L
V RT (0.08314 L bar mol−1 K −1 )(28 + 273)K
#  6.022  1023 molecules   2.0  10−8 mol   1.00 L 
=   3 
V  1 mol  1L   1000 cm 
= 1.2  1013 molecules/cm3
2.91 First, determine moles of liquid oxygen in 150 L. Then, calculate how many moles
of dry air contain this amount of oxygen. Finally, use the ideal gas equation to
calculate the volume:
ISBN 9781119709411
V  103 mL   1.14 g   1 mol 

n = = 150 L     = 5.34  10 mol
3
M  1 L  1 mL  32.00 g 
nO 5.34  10 mol
3
nair = 2 = = 2.55  104 mol
X O2 0.2095
nRT (2.55  104 mol)(0.08314 L bar mol −1 K −1 )(298 K)
V = = = 6.32  105 L
p 1.000 bar
2.92 This is an empirical formula problem, with p–V–T data added to allow calculation of
the molar mass. Use the combustion data to determine the mass percent composition
of the compound, and then use elemental molar masses to find the empirical
formula:
 1 mol   1 mol C   12.01 g 
mC = 363 mg CO 2     = 99.1 mg C
 44.01 g   1 mol CO 2   1 mol 
 99.1 mg 
% C = 100%   = 79.3 %
 125 mg 
 1 mol   2 mol H   1.008 g 
mH = 63.7 mg H 2 O     = 7.13 mg H
 18.02 g   1 mol H 2 O   1 mol 
 7.13 mg 
% C = 100%   = 5.70%
 125 mg 
% O = 100% − (79.3% + 5.70%) = 15.0%
Assume that the sample weighs 100 g and determine the number of moles of each
element in the sample:
 1 mol 
C: 79.3 g   = 6.60 mol C
 12.01 g 
 1 mol 
H: 5.70 g   = 5.65 mol H
 1.008 g 
 1 mol 
O: 15.0 g   = 0.938 mol O
 16.00 g 
Divide each by the smallest among them, 0.938 mol O, to determine the relative
amounts of each:
6.60 mol C
= 7.04 C/O, round to 7
0.938 mol O
5.65 mol H
= 6.02 H/O, round to 6
0.938 mol O
The empirical formula is C7H6O, with the following molar mass:

M = 7(12.01 g/mol) + 6(1.01 g/mol) + 16.00 g/mol = 106 g/mol
Determine the actual molar mass using the ideal gas law. First convert all properties

ISBN 9781119709411
of the vapour into the units of R:

 1g 
m = 110 mg  3  = 0.110 g
 10 mg 
T = (150 + 273.15 K) = 423 K
mRT (0.110 g)(0.08314 L bar mol −1 K −1 )(423 K)
M= = = 106 g/mol
pV (0.365 bar)(0.100 L)
The molar mass is the same as the empirical molar mass, so the molecular formula
is the same as the empirical formula.
2.93 In addition to a yield problem, information is given about both starting materials, so
this is a limiting reactant problem that involves gases. We must calculate the
number of moles of each species, construct a table of amounts, and use the results
to determine the theoretical yield. Water can be ignored, because CH4 is the product
of interest. All of the reagents of interest are gases, so pressures can be used as the
measures of amounts:
Reaction: 3 H2 (g) + CO (g) → CH4 (g)

Initial pressure (bar) 20.0 10.0 0.0
Change (bar) –20.0 –6.67 +6.67
Final pressure (bar) 0.0 3.33 6.67
Use the ideal gas equation and mole–mass conversion to obtain the theoretical yield in
grams:
pV (6.67 bar)(100 L)
n = = = 14.0 mol
RT (0.08314 L bar mol−1 K −1 )(575 K)
Theoretical amount = nM = (14.0 mol)(16.04 g/mol) = 225 g
Obtain the percent yield by dividing the actual yield by the theoretical yield:
 145 g 
% Yield = 100%   = 64.4%
 225 g 
2.94 (a) This part is a stoichiometry problem. From the balanced equation, every 2 mole
of TNT yields 12 + 5 + 3 = 20 moles of gases. MTNT = 227.14 g/mol:
 103 g  1 mol   20 mol gas 
ngas = 1.0 kg     = 44 mol
 1 kg   227 g   2 mol TNT 
(b) Use the ideal gas equation to obtain the volume:
(44 mol)(0.08314 L bar mol −1 K −1 )(298 K)
V= = 1.1103 L
(1.00 bar)

ISBN 9781119709411
(c) Determine mole fractions by dividing moles of that gas by the total number of
moles. Then use the calculated mole fractions to obtain the partial pressures:
X CO = (12/20) = 0.60 X H2 = (5/20) = 0.25 X N2 = (3/20) = 0.15
pCO = (0.60)(1 bar) = 0.60 bar pH2 = 0.25 bar pN2 = 0.15 bar
2.95 The chemical reaction is N2 + 3 H2 → 2 NH3. The molecular picture shows 4 moles
of N2 and 12 moles of H2, which represents stoichiometric proportions. If the
reaction goes to completion, all molecules will react to form 8 moles of NH3:
2.96 This is an example of an ideal gas thermometer. Because n and V are fixed,
p nR
= = constant
T V
T p (273 K)(0.993 bar)
Tf = i f = = 589 K Tf = 589 K − 273.15 = 316°C
pi (0.460 bar)
2.97 The question looks like an empirical formula problem, but the only data provided
are p–V–T data for the gaseous substance, which suggests that an ideal gas law
m
calculation can be done. Use the gas data to calculate n, and then use n = to
M
determine M and subsequently determine the formula of the compound:
pV (0.736 bar)(0.100 L)
n = = −1 −1
= 2.92  10−3 mol
RT (0.08314 L bar mol K )(30 + 273 K)
m 0.500 g
M = = = 171 g/mol
n 2.92  10−3 mol
The compound contains one nickel atom (M = 58.69 g/mol) and x CO molecules (M =
28.01 g/mol), so 171 g/mol = 58.69 g/mol + (x)(28.01 g/mol)
171 g/mol − 58.69 g/mol

x= =4 The formula is Ni(CO) 4
28.01 g/mol
2.98 The only things that are changing in the problem are the number of moles (which is
halved), temperature, and pressure. Volume is constant:

ISBN 9781119709411
nf Tf pi (1 mol)( − 5 + 273 K)(0.921 bar)

pf = = = 0.417 bar
niTi (2 mol)(23 + 273 K)
2.99 At the top of Mount Everest, the atmospheric pressure is 0.333 bar, much lower than
the pressure at sea level, 1.01 bar. A lower pressure corresponds to a smaller
molecular density. Thus, when people say “the air is thin,” they are referring to the
fact that air is less dense at higher elevations.
2.100 (a) Each container contains the same number of gas molecules. Because Container
A has half the volume as Container B, it will have twice the pressure.
(b) Container A has the higher partial pressure of molecular hydrogen. Container A
has five molecules of H2 and Container B has eight molecules of H2 but twice
the volume. Thus, Container A has a higher number of molecules per unit
volume, producing a higher partial pressure of H2.
(c) The graph shows one large peak and one small peak, indicating an unequal
amount of two different species. The lighter gas, molecular hydrogen, will take
less time to reach the detector. The first peak is the larger peak, indicating that
the container with a greater proportion of molecular hydrogen, Container B, is
the one used in the experiment.
2.101 There are two interconnected parts to this problem. Calculate moles of oxygen
using the ideal gas equation, and then use stoichiometric analysis for KClO3:
(a) Begin by converting all values into units matching those of R:
 10−3 L 
V = 22.96 mL   = 0.02296 L
 1 mL 
T = (25.17 + 273.15) K = 298.32 K
pV (1.012 bar)(0.02296 L)
n= = −1 −1
= 9.370  10−4 mol
RT (0.08314 L bar mol K )(298.32 K)
(b) The balanced reaction is: 2 KClO3 → 2 KCl + 3 O2
 2 mol KClO3 
nKClO3 = (9.370  10−4 mol O2 )  −4
 = 6.245  10 mol
 3 mol O2 
(c) mKClO3 = nM = (6.245  10−4 mol)(122.55 g/mol) = 7.654  10−2 g
 mKClO3   7.654  10−2 g 
% KClO3 = 100%   = 100%   = 72.62%
 mtotal   0.1054 g 
2.102 This is an empirical formula problem, with p–V–T data added to allow calculation
of the molar mass. First, determine the empirical formula from mass percentages.
Consider 100 g of the compound, which contains the following amounts:

ISBN 9781119709411
 1 mol   1 mol 
C: 71.22 g   = 5.930 mol C H: 14.94 g   = 14.82 mol H
 12.011 g   1.0079 g 
 1 mol 
N: 13.84 g   = 0.9881 mol N
 14.007 g 
Divide each by the smallest among them, 0.9881 mol N:
 5.930 mol C 
C:   = 6.001 mol C/mol N, round to 6 C/N
 0.9881 mol N 
 14.82 mol H 
H:   = 15.00 mol H/mol N
 0.9881 mol N 
Empirical formula: C6H15N, empirical M = 101 g/mol
Next, use the p–V–T data to determine the actual molar mass:
 10−3 g 
m = 250 mg   = 0.250 g
 1 mg 
 10−3 L 
V = 150 mL   = 0.150 L T = 150 + 273 K = 423 K
 1 mL 
mRT (0.250 g)(0.08314 L bar mol −1 K −1 )(423 K)
M = = = 101 g/mol
pV (0.580 bar)(0.150 L)
The molar mass is the same as the empirical molar mass, so the molecular
formula is the same as the empirical formula.
2.103 There are two interconnected parts to this problem. Use stoichiometric analysis to
calculate the amount of H2O produced, and then use the ideal gas equation to
determine the final pressures:
The reaction is CuSO4•5H2O → CuSO4 + 5 H2O
M CuSO4 •5H 2O = 63.55 g/mol + 32.07 g/mol + 9(16.00 g/mol)
+ 10(1.01 g/mol) = 249.72 g/mol
 1 mol   5 mol H 2 O  −2
nH2O = 2.50 g CuSO 4 •5H 2O    = 5.01  10 mol
 249.72 g   1 mol CuSO 4 •5H 2 O 
(5.01  10−2 mol)(0.08314 L bar mol−1 K −1 )(227 + 273.15 K)
pH2O = = 0.521 bar
4.00 L
For the air in the vessel, the only change from initial conditions is a temperature
change, so

ISBN 9781119709411
piTf (1.00 bar)(227 + 273.15 K)

pf, air = = = 1.67 bar
Ti 300 K
ptotal = 1.67 bar + 0.521 bar = 2.19 bar
2.104 The balloon will rise when its net density is less than that of the air that surrounds
it. Thus,
mair = mHe + 350 kg

mair − mHe = 350 kg
However, the volume of air displaced is the same as the volume of He inside the
balloon, so we have:
airV − HeV = 350 kg

350 kg
V=
air − He
The molar mass of dry air is calculated from the molecular weights of nitrogen and
oxygen, the main constituents of dry air:
 78%   22% 
M air =  (28.02 g / mol)  +  (32.00 g / mol)  = 28.9 g / mol
 100%   100% 
The density of dry air is therefore:
pM (1 bar)(28.9 g / mol)
air = = = 1.17 g / L
RT (0.08314 L bar mol−1 K −1 )(298 )
The density of helium gas under these conditions is
pM (1 bar)(4.003 g / mol)
He = = = 0.162 g / L
RT (0.08314 L bar mol −1 K −1 )(298 )
And so the volume is
350 kg 350  103 g

V= = = 3.47  105 L
air − He (1.17 − 0.162)g / L
2.105 A balloon will rise if its net density is less than that of air. For this to be true, the
total mass of the balloon plus its payload must be smaller than the mass of the air
that it displaces. This gives a mass relationship that must be satisfied:

ISBN 9781119709411
mcool air = mhot air + 350 kg mcool air − mhot air = 3.50 105 g
Use the ideal gas equation to link m with T, the temperature of the hot air:
m pV pVM
n= = m=
M RT RT
Because all these quantities except for temperature are the same for cool air and
hot air, common terms can be collected:
pVM air  1 1 
 −  = 3.50  10 g
5
R  Tcool Thot 
The molar mass of air can be found from the mole fractions of N2 and O2 (minor
components contribute negligibly):
Mair = (0.7808)(28.01 g/mol) + (0.2095)(32.00 g/mol) = 28.6 g/mol
The volume of the balloon is the volume found in Problem 2.115: 3.47 × 105 L
(1.00 bar)(3.47  105 L)(28.6 g/mol)  1 1 

−1 −1  −  = 3.50  10 g
5
(0.08314 L bar mol K )  Tcool Thot 

 1 1  −1
 −  = 0.002932 K Tcool = 298 K
 Tcool Thot 
 1 1  −1
 −  = 0.002932 K Thot = 2.36  103 K
 298 K Thot 
The material of the balloon would probably not withstand this hot a temperature.
Hot air balloons must have much larger volumes than helium balloons per unit
payload.
2.106 As the mouse breathes, it inhales air containing oxygen. Some of this oxygen is
used for metabolism, resulting in CO2, which the mouse exhales. The amount of
oxygen consumed is therefore equal to the amount of CO2 exhaled. The solid KOH
in the chamber absorbs all the CO2 and any water the mouse exhales. Any reduction
in pressure is therefore due to the removal of oxygen from the atmosphere.
The initial amount of gas in the chamber is
pinitialV 1.02 bar(2.05 L)

ninitial = = = 0.08439 mol
RT (0.08314 L bar K −1mol −1 )(298 K)
And after two hours, the amount of gas remaining is
pinitialV 0.967 bar(2.05 L)

ninitial = = = 0.0800 mol
RT (0.08314 L bar K −1mol −1 )(298 K)
The amount of oxygen consumed is therefore 0.08439 – 0.0800 mol = 0.00439 mol.
(0.00439 mol)(32.00 g/mol) = 0.140 g O2.

ISBN 9781119709411
2.107 Think about the final conditions for the bottle. It contains air and helium, with ptotal
= pair + pHe. Each partial pressure must be calculated separately and then summed
for the total pressure. The air pressure can be calculated as a variation in
conditions. Temperature changes, and although the volume of the bottle is fixed,
the gas volume changes because initially there is 0.100 L of liquid helium present.
pV
Thus, = nR = constant.
T
pi = 1.0 bar Vi = 2.00 L − 0.100 L = 1.90 L Ti = 95 K
pf = ? Vf = 2.00 L Tf = 25 + 273.15 = 298 K
 p V   T  (1.0 bar)(1.90 L)(298 K)
pf, air =  i i   f  = = 2.98 bar
 i  f 
T V (95 K)(2.00 L)
The pressure due to helium can be calculated by finding the number of moles of
liquid helium, and then applying the ideal gas law for the final conditions:
m Vd (0.100 L)(103 mL/L)(0.147 g/mL)
n= = = = 3.68 mol
M M (4.00 g/mol)
pHe = = = 45.6 bar
V (2.00 L)
ptotal = 2.98 bar + 45.6 bar = 48.6 bar
2.108 Dry air, according to Table 2-4, has a mole fraction of oxygen of 0.2095. The
amount of oxygen in the pressurized tank is calculated as follows:
p V 
nO2 = X O2 nair = X O2  air air 
 RT 
 (165 bar)(12.5 L) 
= 0.2095  −1 −1  = 82.69 mol O 2
 (0.08314 L bar K mol )(27 + 273) K 
(82.69 mol)(32.00 g/mol) = 2646 g O2.
2646 g O2
At a rate of 14.0 g O2 per minute, the tank will last = 189 min
14.0 g/min
Allowing 6 minutes for surfacing, and neglecting the time required to dive to depth,
you could therefore stay at depth for 183 minutes.
2.109 This is primarily a stoichiometry problem, but a gas law calculation is needed to
determine the volume of gas produced. The reactions are
S (s) + O2 (g) → SO2 (g)
SO2 (g) + CaO (s) → CaSO3 (s)
The reaction stoichiometry is in 1:1 mole ratios, so nS = nSO2 = nCaO = nCaSO3 .
Determine the amount (in moles) of sulphur in the coal, which equals all other

ISBN 9781119709411
amounts:
 103 kg  103 g   4.55% 
mS = 1.00 tonne     = 4.55  10 g S
4
 1 tonne  1 kg   100% 
m 4.55  104 g
n= = = 1.42  103 mol S
M 32.07 g/mol
(1.42  103 mol)(0.08314 L bar mol −1 K −1 )(55 + 273.15 K)
V= = 3.87  104 L
1.00 bar
mCaO = nM = (1.42  10 mol)(56.08 g/mol) = 7.96  104 g
3
mCaSO3 = nM = (1.42  103 mol)(120.2 g/mol) = 1.71  105 g

2.110
pV (L bar)
V (L)
–1
1/V (L )
Pressure, bar
The plot shows that as p increases, V decreases. This is explained by the ideal gas
nRT
equation, V = .
p
The plot of pV versus p is linear and horizontal. According to the ideal gas equation,
pV = nRT . As long as n and T are constant, the product pV will also be constant.
This is also referred to as Boyle’s Law.
The plot of 1/V versus p rises slowly with p. According to the ideal gas law, per

ISBN 9781119709411
1 p
mole, = . 1/V is thus the concentration of the gas; that is, mol/L.
V RT
2.111 As the temperature is increased, the dry ice will sublime, then the pressure will
gradually increase. Although the ideal and van der Waals equation do not predict
the same pressure at all temperatures, we can calculate the temperature at which
they do agree as follows:
From the ideal gas equation:
nRT
pideal =
V
and from the van der Waals equation:
nRT n2
p vdW = -a 2
V-nb V
If the two equations predict the same pressure, then
nRT nRT n2
= -a 2
V V-nb V
rearranging to solve for T and simplifying;
nRT nRT n2
- =a 2
V-nb V V
 nR nR  n2
T - =a 2
 V-nb V  V
n2 n2 an
a 2 a 2
T= V = V = RV 2
 nR nR   1 1  1 1
 V-nb - V  nR  V-nb - V   V-nb - V 
For CO2, a = 364.0 kPa L2 mol-2 = 3.64 bar L2 mol-2; b = 0.0427 L mol-1.
In this problem, V = 50 mL = 0.050 L; n = 36.0 g / 44.0 g mol-1 = 0.818 mol

ISBN 9781119709411
3.64 bar L2 mol 2 (0.818 mol)

0.08314 L bar K −1mol−1 (0.050 L) 2
T=
 1 1 
 0.050 L - 0.818 mol(0.0427 L mol −1 ) - 0.050 L 
 
14325 L K
=
66.35 L − 20.00 L
= 309 K
At this temperature, the ideal gas equation and the van der Waals equation predict the
same pressure, so either can be used to calculate the pressure:
nRT 0.818 mol(0.08314 L bar K −1 mol−1 )(309 K)

p= = = 420 bar
V 0.050 L
2.112 Solving this problem requires using both equation 2-3, which relates kinetic energy
to molecular speed, and equation 2-4, which relates kinetic energy to temperature.
From equation 2-3, we can calculate the kinetic energy of a molecule moving at speed
v:
mv 2
E kinetic = (per molecule)
2
If a collection of atoms has average speed v, then Ekinetic is the average kinetic energy
of these atoms. For a mole of these atoms, the average kinetic energy is therefore:
mv 2
E kinetic = N A (per mole)
2
From equation 2-4, we found that the average molar kinetic energy is related to
temperature:
3RT
E kinetic =
2
Equating these two expressions for kinetic energy and solving for the temperature

ISBN 9781119709411
gives:
mv 2 3RT
NA =
2 2
N A mv = 3RT
2
N A mv 2 Mv 2
T= =
3R 3R
For cesium atoms, M = 0.1329 kg mol-1. Thus,
0.1329 kg mol-1 (0.005 m s -1 ) 2

T= -1 -1
= 1.3 10−7 K
3(8.314 J K mol )

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SOLUTIONS MANUAL FOR CHEMISTRY 4TH CA

Chapter 2 The Behaviour of Gases

Solutions to Problems in Chapter 2

 = 6.07  10 Pa = 0.607 bar

© 2021 John Wiley and Sons Canada, Ltd. 2-1

© 2021 John Wiley and Sons Canada, Ltd. 2-2

collect fixed values on the right.

(c) n, R, T are constant: pV = nRT = constant; piVi = pfVf

Convert temperature to kelvins:

Ti = 25 + 273.15 = 298 K Tf = − 15 + 273.15 = 258 K

© 2021 John Wiley and Sons Canada, Ltd. 2-3

© 2021 John Wiley and Sons Canada, Ltd. 2-4

© 2021 John Wiley and Sons Canada, Ltd. 2-5

7.79  10−2 mol

© 2021 John Wiley and Sons Canada, Ltd. 2-6

9.79  10−2 mol 1.36  10−2 mol

© 2021 John Wiley and Sons Canada, Ltd. 2-7

pCH4 = (0.874)(2.35 bar) = 2.05 bar

2.23 Stoichiometric calculations require moles and a balanced chemical equation.

The unbalanced chemical equation is

C6H12O6 + O2 → CO2 + H2O

Give both CO2 and H2O a coefficient of 6 to balance C and H:

C6H12O6 + O2 → 6 CO2 + 6 H2O;

C6H12O6 (g) + 6 O2 (g) → 6 CO2 (g) + 6 H2O (l)

 1 mol   6 mol CO2  −1

© 2021 John Wiley and Sons Canada, Ltd. 2-8

nRT (1.548  10−1 mol)(8.314 L kPa mol −1 K −1 )(310 K)

2.24 Stoichiometric calculations require moles and a balanced chemical equation.

nRT  (1.92  10−2 mol)(0.08314 L bar mol −1 K −1 )(298 K) 

© 2021 John Wiley and Sons Canada, Ltd. 2-9

Reaction: 2 Na (s) + Cl2 (g) → 2 NaCl (s)

nRT (5.0  10−2 mol)(0.08314 L bar mol−1 K −1 )(320 K)

© 2021 John Wiley and Sons Canada, Ltd. 2-10

The balanced chemical reaction is N2 + 3 H2 → 2 NH3.

piV (137.5 bar)(8.75  103 L)

Reaction: N2 (g) + 3 H2 (g) → 2 NH3 (g)

© 2021 John Wiley and Sons Canada, Ltd. 2-11

© 2021 John Wiley and Sons Canada, Ltd. 2-12

2.32 Molecular speed is related to temperature by the equations,

© 2021 John Wiley and Sons Canada, Ltd. 2-13

2.34 Molecular speed is related to temperature by the equation,

2.35 Average molecular kinetic energy is directly proportional to temperature and is

© 2021 John Wiley and Sons Canada, Ltd. 2-14

2.36 Average molecular kinetic energy is directly proportional to temperature and is

© 2021 John Wiley and Sons Canada, Ltd. 2-15

27oC + 273 = 300 K, Ekinetic, mp = 4.13 × 10–21 J

© 2021 John Wiley and Sons Canada, Ltd. 2-17

© 2021 John Wiley and Sons Canada, Ltd. 2-18

© 2021 John Wiley and Sons Canada, Ltd. 2-19

T = 25.0 + 273.15 = 298. K

(2.55 g)(0.08314 L bar mol−1 K −1 )(298 K)

M = 1(12.0 g/mol) + 2(19.0 g/mol) + 2(35.5 g/mol) = 121 g/mol

This matches the experimental value. The formula is CF2Cl2.

© 2021 John Wiley and Sons Canada, Ltd. 2-20

m pM (1.007 bar)(146.05 g/mol)

T = 27 °C + 273 = 300. K; M = 32.06 g/mol + 6(18.998 g/mol) = 146.0 g/mol. The

© 2021 John Wiley and Sons Canada, Ltd. 2-21

© 2021 John Wiley and Sons Canada, Ltd. 2-22

effusion rate 14 CO 44 g / mol