PDF Thermodynamics Problem Solving in Physical Chemistry Study Guide and Map 1St Edition Kathleen E Murphy Ebook Full Chapter
PDF Thermodynamics Problem Solving in Physical Chemistry Study Guide and Map 1St Edition Kathleen E Murphy Ebook Full Chapter
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Termodynamics Problem Solving in
Physical Chemistry
Termodynamics Problem Solving in
Physical Chemistry
Study Guide and Map
Kathleen E. Murphy
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
and by
CRC Press
2 Park Square, Milton Park, Abingdon, Oxon OX14 4RN
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WORKBOOK
PART 2: The First Law of Thermodynamics: Work (PV) and Heat, as ∆U and ∆H........................................................... 11
Key Points – The First Law .................................................................................................................................................................................................. 11
Example Problems ..................................................................................................................................................................................................................12
Adiabatic Processes ................................................................................................................................................................................................................14
Example Problems ..................................................................................................................................................................................................................14
Key Points – Calorimetry .....................................................................................................................................................................................................15
Example Problems ..................................................................................................................................................................................................................16
Key Points – Hess’s Law Calculation for ∆H.............................................................................................................................................................17
Example Problems ..................................................................................................................................................................................................................17
Key Points – Indirect Methods for ∆H Determination ......................................................................................................................................17
Example Problems ..................................................................................................................................................................................................................18
Key Points – Using Cyclic Diagrams for ∆H ............................................................................................................................................................19
Example Problems ..................................................................................................................................................................................................................19
Key Points – Temperature Dependence of ∆H .....................................................................................................................................................20
Example Problems ..................................................................................................................................................................................................................21
PART 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium ..................................................................35
Key Points – Gibbs and Helmholtz Free Energy ...................................................................................................................................................35
Example Problems ..................................................................................................................................................................................................................37
Key Points – The Chemical Potential and Phase Diagrams ............................................................................................................................43
Example Problems ..................................................................................................................................................................................................................43
Key Points – The Chemical Potential of Real Gases and Fugacity ..............................................................................................................46
Example Problems ..................................................................................................................................................................................................................47
PART 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ...........................49
Key Points – Free Energy of Mixing ..............................................................................................................................................................................49
Example Problems ..................................................................................................................................................................................................................49
v
vi Contents
FINAL ANSWERS
Many students view physical chemistry problem-solving as is much more valuable than for just chemistry and will allow
largely a mathematical exercise, but it is much more than you to be more successful in dealing with new situations
that. Think of the mathematics as just the means to an end of or problems that you will encounter in your professional
being able to explain the origin and prediction of the physi- career. The map will help you get started but completing
cal properties of chemical substances when by themselves the practice exercises in the workbook will help build your
or in chemical mixtures or reactions in all living organisms, confidence and ability to take on different situations. I have
pharmacology, engineering and chemistry. Together, the deliberately chosen a variety of applications for each major
map and workbook can be a real help to you to be successful concept so you can see the “ins and outs” of working with the
in applying thermodynamics-based concepts. Your course concept or equations. I have also tried to address the need
instructor can access the map for you on the instructor for more visual cues for understanding the problem analysis
resources download hub at https://routledgetextbooks.com/ in the Full Solutions available at https://www.crcpress.com/
textbooks/instructor_downloads. The purpose and function Thermodynamics-Problem-Solving-in-Physical-Chemistry-
of the map is to let you know how to “ask the right questions Study-Guide-and-Map/Murphy/p/book/9780367231163.
to get the right answers” to a large number of possible situ- The students in my physical chemistry classes have found
ations involving thermodynamic principles, and to extend the map very helpful and I expect you will have the same
your analytical thinking and diagnostic abilities. This ability experience.
vii
Author
I grew up near Saginaw, Michigan and obtained a B.S. degree department and the College and oversaw the transition of
in Chemistry from Central Michigan University (Mount the College into health-related areas and a major expansion
Pleasant, MI). I then went on to receive a PhD in Physical of the department. I never left the classroom, though, and
Chemistry from the University of Vermont (Burlington, look forward to devoting much more of my time using my
VT) and did postdoctoral work at Rensselaer Polytechnic experience to develop new strategies for students to address
Institute (Troy, NY). I am currently a Professor of Chemistry, their weaknesses in problem-solving and to surmounting
in the Natural Science Department at Daemen College them. My research interests have been the role of oxygen in
(Amherst, NY) and have been teaching general, analytical wound healing and various environmental topics, such as
and physical chemistry for over 40 years. Eighteen of those bioremediation or detection of metals in the soil or water.
years were spent being in an administrative role within the My hobbies include gardening, quilting and reading.
ix
Workbook
Gases and Gas Laws 1
KEY POINTS – GAS LAWS
◾ Te equation of state: PV = nRT Ideal gas: Van der Waals Virial equation
applies to “ideal gases” where
there are either no interactions nRT nRT n2a nRT ˛ nB n2C ˆ
Pideal = PVdW = − 2 Pvirial = ˙1+ + 2 ˘
between particles (at low T’s and V V − nb V V ˝ V V ˇ
P’s) or where the attractive forces
RT RT a RT ˛ B C ˆ
between the gas particles balance Pideal = PVdW = − Pvirial = 1+ +
Vm Vm − b Vm2 Vm ˙˝ Vm Vm2 ˘ˇ
the repulsive forces. Te equation
can be applied to all gases, inde-
pendent of chemical identity.
◾ Real gases show deviations from ideal behavior and introduce factors that depend on the
chemical identity of the gas molecule.
Te van der Waals equation introduces two important factors, the values of which depend on
the chemical identity of the gas:
◾ A correction for the molar volume the gas particles themselves occupy, represented by
the term “b”, which is subtracted from the total molar volume, appears in the frst term
of the equation.
◾ Te second factor, “a”, is a measure of the attractive forces between the gas molecules,
represented by the term “an2/V2 or a/Vm2”, which is subtracted from the adjusted frst
term.
◾ Te a and b values are tabled for each gas as van der Waals constants.
Te virial equation describes gas isotherms as polynomials in V or Vm, where the second virial
coefcient B, can be related to “a” and “b” from the van der Waals equation. Te value of B is very
temperature dependent, diferent for each gas and may be positive or negative. Te third factor,
“C”, in the equation is rarely needed to defne the behavior of a gas.
3
4 Law of Corresponding States
Te values of Z vary with T and can be determined by comparing observed values of P, V or other
gas properties with those predicted by the ideal gas law.
Vm,obs V Pobs
Z= = obs OR Z =
Vm,ideal Videal Pideal
Te ideal gas law allows for the determination of molecular weights or molar masses of gaseous
species, as well as the density of a gas at any P and T combination, if the chemical identity of the
mass of gas m
gas is known, by defning the number of moles as n = = .
molar mass MW or AW
Molar volumes and the density of a gas, both dependent on P and T, are related
through the molar mass, which is independent of P and T since:
˜ g˝ ˜ L ˝ ˜ g ˝
dgas ˛ ˆ × Vm,gas ˛ = MW ˛
° L˙ ° mol ˆ˙ ° mol ˆ˙
Critical constants for gases: the critical pressure, Pc, and critical temperature, Tc,
defne the point at which the liquid state ends for a substance. Any gas above the Pc,
and Tc cannot be condensed to a liquid, but can be in a “supercritical state”. Te critical
constants for a gas are defned by the van der Waals constants:
a 8a
VC = 3b PC = TC =
27b2 27bR
Te law states: “all gases with the same reduced pressure and temperature will have the same
P V T
reduced volume” where the “reduced” variables, are defned as: Pr = Vr = Tr = .
PC VC TC
◾ By using reduced variables, the van der Waals equation becomes independent of chemi-
8Tr 3
cal identity and is expressed as: Pr = − .
3Vr − 1 Vr2
Boyle Temperature: this is the temperature at which a real gas obeys the ideal gas law, over
an appreciable P range, which depends on the value of a and b, the van der Waals constants:
a
TBoyle = TB = .
Rb
EXAMPLE PROBLEMS
1.1 A) Consider that 25.0 g of CH4(g) is contained in a sealed 2.0-L container at 30°C.
What would be the pressure if the gas were:
(a) Acting as an ideal gas?
(b) Acting as a van der Waals gas?
(c) Obeying the virial equation but only when the frst two terms are signif-
cant? (at 30°C, B for CH4(g) = –43.9 cm3-mol−1)
B) If the volume of the gas was compressed isothermally to 200 mL at T = 30°C,
what would the pressure in (a), (b), and (c) become?
1.2 Generally it is true that the term involving C (from the virial equation) can be neglected
as being too small to afect the fnal value of the P or Z.
RT ˛ Bˆ PVm ˛ Bˆ
A) Given that: Pvirial = ˙1+ ˘ and Z = prove that Z = ˙1 + ˘.
Vm ˝ Vm ˇ RT ˝ Vm ˇ
Chapter 1 – Gases and Gas Laws 5
B) Using the equation for Z involving B, calculate the value of Z for 25.0 g of CH4 at
30°C in the two diferent volumes described in Problem 1.1.
C) Which forces have increased in CH4 in the smaller volume – the repulsive or
attractive forces? Give the reason(s) for your choice.
1.3 A) Derive the expression for the density of a gas, assuming it is an ideal gas, in
terms of:
(a) P, molar mass (MW) and T
(b) MW and Vm
B) (a) Defne Z in terms of the observed density of a gas compared to the expected
ideal gas law value, given that Z = Vm,obs Vm,ideal.
(b) What would be true about the observed density of the gas, compared to the
expected ideal value, when Z < 1.0?
(c) What would be true about the observed density of the gas, compared to the
expected ideal value, when Z > 1.0?
1.4 If Z = 0.8808 for CH4(g) at 50°C and 130 atm,
A) What is the density of the gas, assuming that it obeyed the ideal gas laws?
B) What is the actual density of the gas?
1.5 In an industrial process, N2(g) at 300 K and P = 100 atm, weighing 92.4 kg, is heated to
500 K in a sealed container with V = 0.500 m3. What is its fnal pressure, assuming that
the gas acts:
A) As an ideal gas?
B) As a van der Waals gas?
1.6 A) Given the data for NH3 gas in the table on the right:
(a) What is Z for the gas at each tempera-
P (atm) T (K) Vm,obs (cm3/mol)
ture and pressure?
(b) What efect does the increase in pres- I 10 340 2606
sure have on Z? Which forces are being II 25 340 908.2
increased – repulsion or attraction?
B) Estimate the Boyle Temperature for NH3.
1.7 Using the van der Waals constants for CO2, N2, O2, and Ar gases:
A) What value of R should you use for the calculation of the Boyle temperature
from the van der Waals constants? Explain your choice.
B) Calculate the expected Boyle temperature for each of these gases and com-
pare it with the observed temperatures given below.
Gas CH4 N2 H2 Ar
Observed Boyle temperature 510 K 327 K 110 K 411.5 K
1.8 Te density of an ideal gas is found to be 1.8813 g/L at 25°C and 1.00 atm pressure.
What is the molar mass of the gas?
1.9 At 500°C and 699 torr, the density of sulfur gas is 3.71 g/L. A molecular form of sulfur
exists in the gas phase at this T, as Sn.
A) What is the value of n?
B) What is the correct molecular formula for the gaseous species?
1.10 Te density of a gas in a closed container is measured as 3.864 g/L at 1.35 bar and
25°C.
A) If the gas were a diatomic gas, what is the identity of the gas?
B) If the gas were a mixture of Xe and Ar, what is the % by mass of Ar in the
mixture?
6 Example Problems
1.11 A) What are the appropriate units for Pr, Vr and Tr?
B) For the van der Waals equation,
written in reduced variables,
what are the units on the frst
and second terms?
C) If a gas has a molar volume of 15.0
L/mol at 27°C, what would be the
value of its reduced pressure if its
critical values were Pc = 42.7 atm,
Tc =151.5 K and Vc =0.0752 L/mol?
D) Given the graph of Z versus the
reduced pressure on the right,
estimate the value of Z and state
whether the gas is acting as an
ideal gas or not.
E) What would be the pressure of
the gas if we were to assume that it was an ideal gas?
1.12 Given that of a gas has the constant values of a = 0.751 atm L2-mol−2, and
b = 0.0226 L-mol−1:
A) Estimate the critical constants Pc, Vc, and Tc for the gas.
B) What would be the value of Zc?
1.13 A certain gas obeys the van der Waals equation with a = 0.500 Pa m6-mol−2, when its
molar volume is 5.00 × 10−4 m3-mol−1 at 273 K and 3.00 MPa.
A) From this information, calculate the value of b for the gas.
B) What is the value of Z for the gas under these conditions?
1.14 Could 131.0 g of Xe(g), that was in a sealed container with a volume of 1.0 L at 25°C,
exert a pressure of 20 atm if:
A) It acts as an ideal gas?
B) It acts as a van der Waals gas?
C) Considering the same mass of Xe(g) in the sealed container, at what tempera-
ture, in °C, would Xe(g) exert a P = 20 atm if acting as:
(a) An ideal gas
(b) A van der Waals gas?
1.15 An ideal gas undergoes an isothermal compression that reduces its volume by 2.20 L.
Its fnal pressure is 3.78 × 103 torr and its fnal volume is 4.65 L.
A) What was the initial pressure of the gas in atm, assuming the gas acts as an ideal gas?
B) If we had assumed the gas was acting as a van der Waals gas, could we determine
the original pressure from the data given? If yes, then determine the pressure. If
not, explain why you can’t determine the original pressure.
1.16 It is very easy to estimate the molar volume of a gas if it is acting as an ideal gas, with
no intermolecular interactions, but not if it is under conditions that produce real gas
behavior. For example, the van der Waals equation will become a cubic equation if
rearranged to solve for Vm.
˛ RT ˆ a RT 2 a ab
P=˙ ˘− 2 Vm3 − b + Vm + Vm − =0
˝ Vm − b ˇ Vm P P P
Software is available on the internet that can be used to solve for the correct cube root
of the equation. (Resources such as the “cubic equation solver” at CalculatorSoup.com
in the algebra section will solve for the three roots of the cubic equation.)
A) Prove that the van der Waals equation, when rearranged, becomes:
˛ RT ˆ 2 a ab
Vm3 − ˙ b + ˘ Vm + Vm − =0
˝ P ˇ P P
Chapter 1 – Gases and Gas Laws 7
◾ Gases in a mixture, that occupy the same volume at the same temperature, will each
have “partial pressures” that can be summed to obtain the total pressure of the mixture
(Dalton’s Law of Partial Pressures): PTotal = P1 + P2 + P3 + ˜ + Px
◾ Gases do not need to be acting ideally, but always expect partial pressures to be summed.
◾ Use the term “partial pressure” to refect that the gas is part of a gaseous mixture.
n RT n RT
◾ If each gas obeys the ideal gas law P1 = 1 ° Px = x then the mole fraction, χ, as a
V V
° RT ˙ n
pressure ratio can be defned by: Ptotal = ntotal ˝ mix ˇ and P1 = 1 ( Ptotal ) = c1 Ptotall
˛ Vmix ˆ ntotal
◾ If gases are at the same P and T, as in a chemical reaction, VTotal = V A + V B + VC + VD then
° RT ˙ n V
the volumes add: VTotal = V1 + V2 +˜ + Vx Vmix = ntotal ˝ mix ˇ and A = c A = A
˛ Ptotal ˆ ntotal Vtotal
◾ For any two gases in the reaction, the stoichiometric ratio is defned by the volume ratio
of the reaction volumes needed or the product-to-reactant ratios [Law of Combining
Volumes]:
nA a V A nD d V D
= = OR = =
nB b V B nB b V B
EXAMPLE PROBLEMS
1.18 If 250 g of Cl2 and 150 g of C2H6 gases are added to a 10-L container at 30°C, what is the
total pressure if both gases are acting as:
A) Ideal gases?
B) van der Waals gases?
1.19 Carbon monoxide competes with O2 for binding sites on hemoglobin, but, once bound,
CO molecules are not as easily removed as are O2 molecules, so that CO poisoning
is really a lack of O2 or sufocation. A safe level of CO is 50 ppm, with symptoms of
poisoning appearing at 800 ppm, and death occurring within 30 minutes if the level
8 Example Problems
reaches 3200 ppm. Taking the partial pressure of O2 as 0.20 in air, what is the ratio of
molecules of O2 to CO when the level is 50 ppm, 800 ppm and 3200 ppm CO?
[Note: 1 ppm = 1 g pollutant per cubic meter of air]
1.20 In normal respiration, an adult exhales about 500 L per hour. If the exhaled air is satu-
rated with water vapor at 37°C, where the equilibrium vapor pressure is 0.062 atm,
what mass of water is exhaled in one hour?
1.21 Te total pressure of a mixture of O2 and H2 gases is 1.00 atm. Te mixture is ignited
and liquid water produced, which is then removed. Te remaining gas is pure H2 and
has a P = 0.400 atm when measured at the same V and T of the original mixture. What
was the composition of the original mixture in mole percent?
1.22 A rigid vessel with a volume of 5.0 L that contains 500 g of CO2(g) at 20.5°C is con-
nected through a stopcock valve to a second rigid vessel with a volume of 500 cm3, that
contains 35.5 g of Ar(g) at 20.5°C. After the valve is opened to allow the gases to mix:
A) If the gases act ideally, what is:
(a) Te mole fraction of CO2 in the mixture after opening the valve?
(b) Te partial pressure of each gas in the mixture?
(c) Te total pressure in the vessels after the valve has been opened?
B) What would have been the answers to (b) and (c) if you consider the gases to be
van der Waals gases instead of ideal gases?
C) One of the gases does not significantly change pressure when treated as
a van der Waals gas. What would be the main factor(s) that make it stay
unchanged?
1.23 A gas mixture containing 5 mol % butane, C4H10, and 95 mol % Ar (such as is used in
Geiger-Müller counter tubes) is to be prepared by allowing the gases to fll a 40.0-L
evacuated cylinder at 1 atm pressure. Te cylinder is then weighed after each gas is
introduced.
A) Calculate the mass of each gas that needs to be added to produce the desired
composition when the temperature is maintained at 25.0°C.
B) Determine the density of the fnal mixture of gases.
1.24 An ideal gas mixture contains 320 mg CH4(g), 175 mg Ar(g), and 225 mg Ne(g) at
300 K. If the partial pressure of Ne is 66.5 torr in the mixture, what is:
A) Te total pressure in torr?
B) Te total volume of the mixture?
1.25 Mount Pinatubo erupted in 1991 with the second largest volcanic eruption in the
20th century. It spewed 20 million tons of SO2(g) into the high atmosphere where the
T = −17°C. If the volume of the atmospheric layer it entered (the troposphere) is approx-
imately 8.0 × 1018 m3, what was:
A) Te partial pressure of SO2 in the atmosphere?
B) Te mole % of SO2 in the atmosphere?
1.26 A mixture of HCl(g), H2(g), and Ne(g) used for lasers is 5.00% (w/w) HCl, and 1.00%
(w/w) H2, with the rest being Ne. Te mixture is sold in cylinders that have a volume of
49.0 L and P = 138.0 kPa.
A) What is the mole fraction of each gas in the mixture?
B) What is the pressure of each gas in the mixture?
C) What is the total mass of gas in the fask?
Chapter 1 – Gases and Gas Laws 9
◾ Te change in internal energy of a system can be defned as the sum of the changes in
work, dw, and thermal energy, heat, dq.
U = q + w ˛ dU = dq + dw
◾ Enthalpy, H is defned as: H = U + PV and represents changes in thermal energy that are
measured under constant-pressure conditions, as qP. Te heat capacity measured under
constant P conditions, CP, is used to calculate qP.
◾ For gases that undergo the same change in temperature, ∆H and ∆U, will not be equal
to each other since CP ≠ CV.
Later in this section, the criteria that apply to ∆H and ∆U for chemical changes under iso-
thermal conditions will be described, but, frst, we will deal with situations where no chemical
changes are occurring.
EXAMPLE PROBLEMS
2.5 If 3.0 moles of an ideal gas are compressed isothermally from 60.0 L to 20.0 L, with a
constant external pressure of 5.00 atm, what would the values of w, q, ∆U, and ∆H for
the compression?
2.6 Consider the isothermal expansion of 5.25 mol of an ideal gas at 450
K from an initial pressure of 15 bar to a fnal pressure of 3.50 bar,
taking into account the fgures on the right.
A) Describe the process in terms of what changes in P and V must
be carried out that would result in the greatest amount of work
being done by the system and calculate this maximum amount
of work done.
B) Describe the process in terms of what changes in P and V must
be carried out that would result in the least amount of work
being done by the system and calculate that work done.
2.7 A sample of blood plasma occupies 0.550 L at 0°C and 1.03 bar. Te
plasma can be compressed isothermally by a constant pressure of 95.2
bar to a volume that is 94.5% of the original volume.
A) Treating the plasma as if it were acting as a gas, how much
work was done by the surroundings to compress the cells?
B) If the same amount of work was applied to the same volume of
a gas such as N2(g), starting at the same pressure and tempera-
ture, that was compressed with a constant pressure of 10 atm,
what would the fnal volume be?
2.8 Determine the diference in the amount of reversible work that could
be done by the expansion of 2.0 moles of H2(g) at 273 K if it were
treated as a real (virial) gas instead of an ideal gas, given B = 13.7 cm3/
mol for H2(g) at 273 K.
2.9 Suppose 2.25 moles of an ideal gas at 35.6°C expands isothermally from 26.0 dm3 to
70.0 dm3.
A) What was the initial pressure of the gas in bars?
B) Calculate the work done if the expansion occurs against a constant pressure of
0.825 bar.
C) Calculate the work done if the expansion is accomplished reversibly and
isothermally.
P
D) Prove that, for an ideal gas, wrev = −nRT ln 1 and then show that it produces the
P2
same magnitude and sign of reversible work as in question C).
2.10 When 229 J of energy is supplied as heat to 3.0 mol of an ideal gas at constant P, the T
increases by 2.55 K. Calculate the:
A) CP,m for the gas.
B) CV,m for the gas.
2.11 Consider the two situations in the fgure on the right.
Both Apparatus A and B contain equal masses of
ethane, C2H6(g), and O2(g) in sealed containers with
pistons. Flask A has a mass M sitting on its piston,
while B has two stops on the side of the fask that
prevent the piston from moving. Suppose complete
combustion takes place at a constant temperature.
A) For Flask A:
(a) Will the piston move from its original position after the reaction is com-
plete? Explain your answer.
(b) If the piston moves, will the motion be up or down, compared to its original
position?
(c) Can the pressure stay constant during the process, as well as temperature?
Explain the reasoning for your choice.
14 Adiabatic Processes
B) For Flask B:
(a) What will happen to the pressure in the fask before and after the reaction
is complete?
(b) If the heat fow out of Flask B was measured, how would it compare to the
heat fow measured for Flask A?
C) How would the ΔU for the two chemical changes in the fasks compare?
ADIABATIC PROCESSES
◾ For ideal gases, the Joule Tomson coefcient is zero and there is no change from
expected behavior given in the box above.
◾ When a real gas is below its Joule Tomson inversion temperature, the coefcient will
be positive and the expected change, of cooling when expanding, will occur.
◾ If, however, the real gas is above its Joule Tomson inversion temperature, the coef-
fcient is negative and the gas will warm when it expands, not cool.
Tis will be explained in more detail in the section before pressure changes and the efect on ∆H
is considered.
EXAMPLE PROBLEMS
2.12 A) Calculate the work for the reversible adiabatic expansion of 1.0 mole of an ideal
gas with Cp = 5/2 R at an initial pressure of 2.25 bar from an initial temperature
of 475 K to a fnal temperature of 322 K.
B) What would the fnal pressure of the gas have to be if the same work was done
but for an isothermal reversible expansion, if T had been kept constant at 322 K
and the initial P was 2.25 bar?
2.13 What would the fnal T be if 2.0 moles N2(g), initially at 30.0°C, were compressed from
6.0 to 2.0 L:
A) Adiabatically and irreversibly at a constant P of 1.0 atm?
Chapter 2 – The First Law of Thermodynamics 15
−qlost = qgain
Based on this situation, you must determine how the loss and gain occurs,
whether through chemical change, involving a ∆H or ∆U to defne q, or whether
16 Example Problems
it undergoes a temperature change, which will involve using Cp or Cv to defne q. Substituting cor-
rectly for qlost and qgain into the equation will then let you solve for the unknown.
In bomb calorimetry, ∆Ucomb is measured, not ∆Hcomb. Ten the relationship, based on the
gases acting ideally, would be: ˜H comb = ˜U comb + ˜n( RT ).
To calculate ∆H you must know ∆n for the reaction and assume that the reaction happens at the
initial temperature, before the temperature of the water changed, so that you can determine ∆Hcomb.
EXAMPLE PROBLEMS
2.19 A sample of an organic liquid weighing 0.700 g was burned in a bomb calorimeter, for
which the heat capacity of the calorimeter is 2753 J/K and 0.9892 kg of H2O(l) placed in
the calorimeter. Te observed temperature change was from 25.00°C to 28.11°C.
A) Calculate the ∆U per gram for the combustion.
B) If the liquid was propanone, CH3COCH3, determine the ∆Hcomb per mole of pro-
panone from ∆U (assuming H2O(l) is formed in the combustion). Does it match
the tabled value?
C) Why did you need to know the identity of the liquid to answer question B), but
not A)?
2.20 Seven grams of propene, C3H6(g), are burned in a constant-volume calorimeter to form
CO2(g) and H2O(g) at 25°C. Te temperature of the calorimeter and its contents was
observed to rise 13.45°C during the process.
A) Calculate the heat capacity of the calorimeter and its contents in kJ/K.
B) If the state of the water product had been assumed to be liquid, how would the
calorimeter constant value change?
2.21 Substances with large positive or negative enthalpies of solution have commercial
applications as instant cold or hot packs. Single-use versions of these products involve
the dissolution of either anhydrous calcium chloride (CaCl2, ΔHsoln = –81.3 kJ/mol) for
an instant “hot pack” or ammonium nitrate (NH4NO3, ΔHsoln = +25.7 kJ/mol) for a “cold
pack”. Both types consist of a fexible plastic bag that contains liquid water and an
inner pouch of the dry chemical. When the pack is twisted and/or struck sharply, the
inner plastic bag of solid salt ruptures, and the salt dissolves in the water.
A) Considering that 40.25 g of CaCl2(s) is in the inner package, what would be the
temperature change in the 100 mL of water, initially at 22°C, assuming no heat
loss to the surroundings, when it dissolves? (density H2O(l) at 22°C = 0.997 g/mL).
B) What is the maximum mass of NH4NO3 which should be enclosed in a cold pack
containing 100 mL of H2O(l) at 22°C, if you don’t want it to freeze when the solid
fully dissolves? Given the solubility of NH4NO3 is 119 g per 100 mL of water,
would all the calculated amount dissolve?
C) Why can this situation be considered to be a constant P process, so ∆H can be
used for q, and not a constant-volume process, if the package is sealed?
2.22 Complete combustion of 1.0 L of a natural gas mixture of CH4(g) and ethane, C2H6(g),
at 0.0°C and 1.0 atm gives of 43.6 kJ of heat, producing CO2(g) and H2O(l). If the prod-
uct and reactant gases are at same P, T for the combustion, what is the % composition
of the mixture by volume?
2.23 Propane gas, C3H8(g), is kept in a 200-L tank at a pressure of 2.35 atm at 26°C. Some
gas is withdrawn and burned in excess O2(g) until the tank pressure in the gas drops to
1.10 atm. Some of the heat from the combustion was used to heat 132.5 L of water from
26.0°C to 62.2°C.
A) Assuming the combustion products are CO2(g) and H2O(l), what is ∆Hcomb of
the gas at 25°C?
B) Assuming ∆Hcomb is constant, what % of the heat from the combustion is used to
heat the water?
2.24 Suppose someone had proposed an “ice diet”, where energy absorbed by ice melting
would consume the excess Calories (1 Cal = 4.184 kJ) from eating too much food. A
typical daily intake of energy needs to be about 2500 Calories.
Chapter 2 – The First Law of Thermodynamics 17
A) How many kilograms of ice at 0°C would you have to consume and melt at 0°C
to consume 500 Calories, if you consider only the melting process?
B) How would the amount of ice change if you include the heating of the melted
water to 37°C? Is it wise to ignore it?
2.25 Lime, CaO, reacts with water to form Ca(OH)2(s) as the only product:
When 56.0 g CaO is added to 100 mL H2O(l) in an insulated container at 26°C and
1 atm, and a complete reaction occurs, if the heat is absorbed by any liquid water left
in the container, what will be the number of moles of each substance in the container
at the end of the reaction, the fnal temperature and the state of each substance? (Ignore
the solubility of Ca(OH)2 in water and assume that there is no heat lost or gained from
the surroundings.)
EXAMPLE PROBLEMS
2.26 Te hydrocarbon liquid, hexadecane, C16H34, has a heat of combustion equal to –10,700
kJ per mole at 298.15 K and 1.0 bar. Given the products of the combustion reaction are
H2O(l) and CO2(g), what would be the:
A) Standard enthalpy of formation for hexadecane, C16H34, in kJ per mole?
B) Te ∆Ucomb for hexadecane, C16H34, at 298.15 K and 1.0 bar?
C) As an alkane, hexadecane would be close in structure to the lipids or fat biomol-
ecules. Compare the caloric content of hexadecane, C16H34, to that of an average
fat, which is 9.0 kcal/g.
2.27 Te temperature rise of 955 g H2O(l), measured in a constant-pressure calorimeter, was
7.03°C at 1.0 bar when 10.52 g of solid glucose, C6H12O6(s), was completely reacted with
oxygen gas, at 22°C and 1.0 bar, so that it produced pyruvic acid, CH3COCO2H, and
H2O(l).
A) Write the balanced reaction occurring.
B) What is the standard enthalpy of pyruvic acid in kJ/mol from these data? [Given
Cp, H2O(l) = 4.184 kJ/°C-kg]
To correctly add the reactions, you must frst know the balanced reaction you
STEPWISE ADDITION of KNOWN REACTIONS want to determine ∆Hr for. Ten, focus on the substances that are “unique” –
a × (reaction 1) a × ∆H1 that is, which appear in the reaction you want and in ONLY ONE of the listed
+ b × (reaction 2) b × ∆H2 reactions. To get that substance on the correct side of the reaction arrow, you
+ c × (reaction 3) c × ∆H3 may have to reverse the reaction (which will change the sign on the ∆H for
that reaction) and possibly multiply by either a whole number or a fraction in
Summed reaction: reactants → products order to match the coefcient for that substance in the overall fnal reaction
∆Hsummed reaction = a∆H1 + b∆H2 + c∆H3 you seek.
EXAMPLE PROBLEMS
2.28 Te enthalpy of hydration for a salt like sodium acetate trihydrate can be determined by
comparing the enthalpy of solution of anhydrous sodium acetate and that for sodium
acetate trihydrate solids.
H2 O
NaC 2H 3O2 ˜ 3H 2O(s) °°° ˛ Na + (aq ) + C 2H 3O2 − (aq ) + 3H 2O(l) ˇH soln = 19.
9 66 kJ
A) Show how to add the reactions to determine the enthalpy of hydration per mole
of sodium acetate for the trihydrate form.
B) Ten, calculate the enthalpy of hydration in kJ per mole of water for the hydrate.
2.29 Calculate the standard enthalpy for the fermentation of glucose solid, C6H12O6(s),
which produces C2H5OH(l) and CO2(g): C 6H12O6 (s) ® 2C 2H5OH(l) + 2CO2 (g) from
the heats of combustion of ethanol liquid and glucose solid.
2.30 Te molecule, OH(g), is a free radical that is called the “detergent” molecule of the
atmosphere. It reacts with many hydrocarbons or other molecules that enter the atmo-
sphere to oxidize them into forms that can be removed from the atmosphere. It is
present in very low concentrations at any time in the atmosphere, so that the thermo-
dynamics of its production are difcult to measure directly.
A) Given the enthalpy of the following reactions, determine the ∆H for the reac-
tion: H2O(g) → H(g) + OH(g) by adding the appropriate reactions.
Reaction 1: ½ H2(g) + ½ O2(g) → OH(g) ∆H = 38.95 kJ
Reaction 2: H2(g) + ½ O2(g) → H2O(g) ∆H = –241.8 kJ
Reaction 3: H2(g) → 2 H(g) ∆H = 496.0 kJ
Reaction 4: O2(g) → 2 O(g) ∆H = 498.3 kJ
B) In which of the listed reactions would the ∆H be an enthalpy of formation, ∆H°f,
and in which would the ∆H be defned as a ∆Hdissociation or bond energy?
2.31 Te combustion of elemental boron, B(s), produces B2O3(s) as the only product and
releases 1274 kJ of heat per mole. Te combustion of diborane, B2H6(s), yields H2O(l)
and B2O3(s) and has an enthalpy of –2034 kJ per mole.
A) From these two combustion equations and any other defned reactions with
known enthalpies, calculate the ∆H°f of diborane, B2H6(g).
B) Show that solving the problem by using Hess’s Law for the combustion and rear-
ranging to solve for the ∆H°f of diborane, B2H6(g), produces the same result.
2.32 Choose the appropriate reactions and then describe the route to calculate the ∆H by
adding those reactions to produce the ∆Hr for: CS2(l) + 3 Cl2(g) → CCl4(l) + S2Cl2(l)
Reaction I: CS2(l) + 3 O2(g) → CO2(g) + SO2(g) ∆HI = –1077 kJ
Reaction II: 2 S(s) + Cl2(g) → S2Cl2(l) ∆HII = –58.2 kJ
Reaction III: C(s) + 2 Cl2(g) → CCl4(l) ∆HIII = –135.4 kJ
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