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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
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Boca Raton, FL 33487-2742
and by
CRC Press
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© 2020 by Taylor & Francis Group, LLC

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No claim to original U.S. Government works
Printed on acid-free paper
International Standard Book Number-13: 978-0-367-23116-3 (Paperback)

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Tis book contains information obtained from authentic and highly regarded sources. Reasonable eforts have been made to publish reliable data and informa-
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Contents
Preface ........................................................................................................................................................................................................................................................................... vii

Author..............................................................................................................................................................................................................................................................................ix
WORKBOOK
PART 1: Gases and Gas Laws ................................................................................................................................................3

Key Points – Gas Laws ............................................................................................................................................................................................................. 3
Law of Corresponding States ............................................................................................................................................................................................. 4
Example Problems .................................................................................................................................................................................................................... 4
Key Points – Mixtures of Gases .......................................................................................................................................................................................... 7
Example Problems .................................................................................................................................................................................................................... 7
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
Key Points – Calorimetry .....................................................................................................................................................................................................15
Key Points – Hess’s Law Calculation for ∆H.............................................................................................................................................................17
Key Points – Indirect Methods for ∆H Determination ......................................................................................................................................17
Key Points – Using Cyclic Diagrams for ∆H ............................................................................................................................................................19
Key Points – Temperature Dependence of ∆H .....................................................................................................................................................20
PART 3: Second and Third Law of Thermodynamics, ∆S ................................................................................................25

Key Points – The Second Law ..........................................................................................................................................................................................25
Key Points – Real Gases and Entropy ...........................................................................................................................................................................33
PART 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium ..................................................................35
Key Points – Gibbs and Helmholtz Free Energy ...................................................................................................................................................35
Key Points – The Chemical Potential and Phase Diagrams ............................................................................................................................43
Key Points – The Chemical Potential of Real Gases and Fugacity ..............................................................................................................46
PART 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ...........................49
Key Points – Free Energy of Mixing ..............................................................................................................................................................................49
v
vi Contents
Key Points – ∆G and Two-Component Liquid Mixtures..................................................................................................................................50

Key Points – Real Solutions and Excess Thermodynamic Functions for Mixtures ...........................................................................51
Key Points – Vapor Pressure, Raoult’s Law, and Henry’s Law for Mixtures ............................................................................................57
Key Points – Henry’s Law for Binary Mixtures.........................................................................................................................................................58
Key Points – Liquid–Vapor Phase Diagrams ............................................................................................................................................................59
Lever Rule Liquid Vapor Diagrams .........................................................................................................................................................................60
Key Points – Non-Ideal or Regular Solutions: Azeotropes ..............................................................................................................................60
Key Points – Activity and Activity Coefcients for Mixtures..........................................................................................................................61
Key Points – Colligative Properties................................................................................................................................................................................67
Key Points – Activity Coefcients in Colligative Properties for Real Solutions ...................................................................................71
Key Points – Henry’s Law and Saturated Solutions of Solute B in A .........................................................................................................73
PART 6: Free Energy, Equilibrium Constants, and Electromotive Force .......................................................................77

Key Points – Free Energy and Chemical Reactions .............................................................................................................................................77
Key Points – Ionic Strength, Activity Coefcients, and Efect on Equilibria .........................................................................................82
Key Points – Electrochemistry, Equilibrium, and Activities............................................................................................................................ 84
Electrochemistry and Equilibrium in Biochemical Redox Reactions .......................................................................................................87
Key Points – Thermodynamics of Redox Reactions: ∆S° and ∆H°...........................................................................................................90
Mean Ionic Activity and Redox Reactions ................................................................................................................................................................91
FINAL ANSWERS
Answers to Example Problems..........................................................................................................................................95

Final Answers and Hints ......................................................................................................................................................................................................95
Part 1: Gases and Gas Laws .........................................................................................................................................................................................95
Part 2: First Law of Thermodynamics – Work (PV), Heat, ∆U and ∆H...............................................................................................96
Part 3: Second and Third Laws – Entropy .......................................................................................................................................................100
Part 4: Free Energy (∆G), Helmholtz Energy (∆A), and Phase Equilibrium .................................................................................. 103
Part 5: Free Energy (∆G) of Mixing, Binary Liquid Mixtures, Colligative Properties, and Activity ..................................109
Part 6: Free Energy (∆G), Equilibrium, and Electrochemistry ...............................................................................................................119
Index .................................................................................................................................................................................. 127

Preface
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.
◾ Te compressibility factor, Z, is a useful parameter with which to determine when a gas

is NOT acting ideally, since
Z < 1.0 The gas is not acting ideally and Gas A

attractive forces dominate. PV PVm
Real gas
Z= =
Vm,obs < Videal
attractive
RT RT
forces
Z = 1.0 The gas is acting ideally dominating B
Z = 1+
Vm,obs = Videal Real gas Gas B Vm
Z > 1.0 The gas is not acting ideally and ideal gas Z = 1+ B ˛P + C ˛P 2
repulsive forces dominate.
Vm,obs > Videal
Real gas Gas C
repulsive forces
dominating
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
LAW OF CORRESPONDING STATES
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
B) Cylinders of compressed O2 gas are typically filled to a pressure of 200 bar

at 25°C. What would be the molar volume of the O2(g) if the gas were acting
as an:
(a) An ideal gas?
(b) A van der Waals gas?
C) Based on the diference in the values for molar volume in A and B, do you expect
that O2(g) is acting as an ideal gas or a real gas in the tank? Briefy, give the
reason(s) for your choice.
1.17 It is not difcult to defne the density of a gas using the ideal gas law. However, it is
more difcult for real gases, unless Z is known (Problem 1.3). Show that it is possible
to fnd the density by deriving an appropriate equation for the density of a real gas
using:
A) A modifed van der Waals equation obtained by assuming V – nb ≈ V for the
nRT an2
conditions of the gas so that we can start from: PVdW = − 2
V V
nRT ˛ nB ˆ
B) Te virial equation, as PVirial = 1 +
V ˙˝ V ˘ˇ
C) Compare the values of density you would calculate using the ideal gas law and
the equations for real gases derived in (A) and (B) for dgas for Cl2(g) at P = 1.00
atm and T = 300 K.
KEY POINTS – MIXTURES OF GASES
◾ 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?
1.27 Suppose the apparatus on the right contains

three diferent gases that have the conditions
given on the diagram. Assuming the volume
of the connecting tubes to be negligible, com-
pared with the bulb volumes, what would be:
A) Te pressure in each bulb after the valves
are opened and equilibrium is estab-
lished, if the gases act as ideal gases?
B) Te mole fraction of each gas in Bulb A?
1.28 Given that dry air, which is 78.08% by mass
N2(g), and 20.95% by mass O2(g) (with the rest
being other gases), and has a density of 1.146
g/L at 740 torr and 27°C, determine :
A) Te partial pressure of N2(g) and its mole
fraction in the air.
B) Te partial pressure of O2(g) and its mole fraction in the air.
1.29 Ammonium nitrate, NH4NO3(s), which is used as a fertilizer, is very explosive at
high temperatures due to its decomposition reaction: 2 NH4NO3(s) → 2 N2(g) + 4
H2O(g) + O2(g). How many liters of gas would be formed by the decomposition of a
40.0-lb bag of NH4NO3(s) at 450°C and 736 torr from 1.0 bar?
1.30 Te reaction of sodium peroxide, Na2O2, with CO2(g), is used in space vehicles to convert
exhaled CO2(g) to O2(g) by the reaction: 2 Na2O2(s) + 2 CO2(g) → 2 Na2CO3(s) + O2(g).
A) Assuming that air is exhaled at an average rate of 4.50 L per minute at 25°C, 736
mm Hg, and that the exhaled air is 3.4% CO2(g) by volume, what is the volume of
CO2 produced daily in the spacecraft?
B) What volume of O2 would be produced daily?
C) How many kilograms of Na2O2 would be needed for a year of conversion?
The First Law of
Thermodynamics
Work (PV) and Heat, as ∆U and ∆H
2
KEY POINTS – THE FIRST LAW
◾ 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
◾ Internal energy, U, is a state function

and its magnitude does not depend
on the pathway, but only on the initial
and the fnal state.
◾ Both dw and dq are pathway depen-
dent, so we must have functions to
defne and integrate the function
from initial to fnal state, to deter-
mine the sign and magnitude of work
and heat.
◾ Both dw and dq are negative in sign
if they fow out of the system during
the change and positive in sign if they
fow into system during the change.
◾ In terms of work, pressure–volume (PV) work is considered at frst, that is: work due to
contraction (+), for work done on the system by the surroundings, or due to expansion
(–), for work done on the system by the surroundings, and is defned as:dw = −PdV .
◾ Tere are two kinds of work, either irreversible or reversible, which produce diferent
functions to evaluate (see map).
◾ Termal energy changes, q or heat, have many diferent defnitions, depending on the
conditions, but can be divided into the broad categories of isothermal changes involv-
ing enthalpy, dH, and non-isothermal changes, where kinetic energy and temperature
changes occur, which involve a heat
capacity, C.
◾ Te relationships and the math that fol-
lows, to determine the magnitude of q,
are summarized on the map, with the
main criteria given.
◾ For temperature changes, it is impor-
tant to assess which conditions, con-
stant pressure or constant volume,
apply when the system involves gases.
◾ Te change in internal energy under
constant-volume conditions involves
no PV work, so then dU = dqV. Te heat
capacity measured under constant V
conditions, CV, is used to calculate qV,
as shown in your textbook and on the
map.
11
12 Example Problems
◾ 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
2.1 Te diagram on the right represents a

series of fve changes of pressure and vol-
ume for 1.0 mol of an ideal gas trapped
in a container with a movable piston.
A) State in which steps:
(1) Work will be done.
(2) Temperature of the gas
must change.
(3) ∆U would be zero
B) If the gas were He(g), what would
be the:
(1) Total work done?
(2) Total q for the changes?
(3) ∆U total for the changes?
C) If the initial temperature of the
gas was 250°C, what will its fnal
temperature be in °C?
2.2 One mole of Ar(g) gas, initially at 20°C
and 1000 kPa, undergoes a two-step
transformation. For each step of the
transformation, calculate the fnal P, q,
w, and ∆U.
STEP 1: Te gas is expanded isother-
mally and reversibly until the volume
doubles.
STEP 2: Ten, the temperature of the gas
is raised to 80°C at a constant volume.
2.3 Two moles of an ideal gas are expanded isothermally and irreversibly from 20 L to 30
L against a constant external pressure. Te total work for the process is found to be
−5065.8 joules.
A) Determine the external pressure in atm present during the expansion.
B) Compute ∆U, ∆H, and q for the process.
C) If the system is at equilibrium at the end of the expansion, what is the tempera-
ture of the system at that point?
2.4 Suppose you started with 2.0 moles of O2(g) at 273 K with a volume of 11.35 dm3(L)
A) What would the ∆U be if the gas temperature was increased to 373 K reversibly
and under constant V conditions?
B) What would the ∆H be if the gas temperature was increased to 373 K reversibly
and under constant P conditions (P = 1 atm)?
C) Prove that the diference between ∆U and ∆H can be explained if you assume
that the gas is ideal, and substitute ∆(nRT) for ∆(PV) in the defnition:
∆H = ∆U + ∆(PV).
Chapter 2 – The First Law of Thermodynamics 13
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
In adiabatic processes, there

ADIABATIC PROCESS: ∆U = dw
is no heat fow into the sys-
∆V(+) then ∆T(−) tem from the surroundings
• gas cools when it expands (q = 0). Typically, either there
∆V(−) then ∆T(+) isn’t enough time for a com-
pensating heat fow in or out
• gas heats when compressed
of the system for work done
on or by the system or the
system is thermally insulated from the
surroundings. As a consequence, an adia-
batic process cannot be isothermal. Tis
condition will impact the amount of work
that is either lost or gained by a gaseous
system for a given volume change.
Te temperature change for a gas
undergoing an adiabatic expansion is also
associated with the Joule Tomson
Coefcient, µJT.
Te sign of the Joule Tomson coef-
˛ dT ˆ cient applies to real gases undergoing an
µ JT = ˙ ˘
˝ dP ˇ H expansion or contraction in an adiabatic
process and determines the sign of the T change.
◾ 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?
B) Adiabatically and reversibly?

Furthermore,
C) Compare the amount of work required for A) and B).
2.14 If 1.0 mole of an ideal gas, with Cp = 5/2 R, that has an initial pressure of 2.25 bar, goes
from an initial temperature of 475 K to 322 K adiabatically:
A) Calculate the fnal volume for the adiabatic expansion
B) Calculate the work for the adiabatic expansion in A).
C) Calculate the work done if the expansion were a reversible expansion.
2.15 Te constant volume heat capacity for a gas and its gamma, γ, the ratio of Cp/Cv, can be
measured by observing how T changes when the gas expands reversibly and adiabati-
cally. If the decrease in pressure is also observed, then the Cv can also be determined.
Given that a fuorocarbon gas doubles its volume when it is reversibly and adiabatically
expanded from 298.15°C to 248.44°C, and the initial pressure was 1522.2 torr:
A) Calculate the value of Cv for the gas.
B) Calculate the value of gamma, γ, for the gas.
˜ ˜ T2 V T P
2.16 A) Given PV 1 1 = P2V2 , prove that C v ln = −R ln 2 ˛ C p ln 2 = −R ln 1 .
T1 V1 T1 P2
B) Ten, given the fnal pressure was 693.5 torr for the gas in (2.12), calculate the
value of Cp in J/mol K for the gas. How close is this value to the value that could
be estimated from γ and Cv calculated in (2.12)?
C) If the gas were acting ideally, the fnal pressure should have been 634 torr.
Estimate the value of Z for the gas.
2.17 When air is compressed with a bicycle pump, its temperature rises, so the process is
adiabatic.
A) If air at 22.0°C and a pressure of 755 torr is pumped into a bicycle tire, with
a total volume of 1.0 L, until a pressure of 65 psi is achieved, what would be
the fnal T of the air in the tire, if an adiabatic compression occurs? (14.7 psi =
1.00 atm)
B) Using the frst law of thermodynamics, explain why the tire heats up.
2.18 A sample of 3.0 mol of an ideal gas at 200 K and 2.0 atm is compressed reversibly and
adiabatically until the T increases to 250 K. Given that CV,m = 27.5 J/K mol for the gas,
calculate:
A) q
B) w
C) ∆U
D) the fnal V of the gas
E) the fnal P of the gas
F) and ∆H for the process
KEY POINTS – CALORIMETRY
Calorimeters, whether open (constant P) systems or closed (constant V) systems,

are designed to be adiabatic and to not allow heat fow to occur between the sys-
tem and surroundings. Terefore, the starting premise is that there are at least
two parts in the system where the heat loss of one defned part of the system
results in an equal gain in another part of the system. So, the mathematical start-
ing point is:
−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.
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:
CaO(s) + H 2O(l) ° Ca (OH )2 (s)
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.)
KEY POINTS – HESS’S LAW CALCULATION FOR ∆H HESS’S LAW

Enthalpy measures the energy changes when interactions or bond- For the general reaction: aA + bB → cC + dD
ing of atoms change in reactions or other processes. Te map lists a
number of diferent types of defned enthalpies and many of these ˜Hr° = ˙ˆc˜Hf°,C + d˜Hf°,D ˇ˘ − ˙ˆa˜Hf°, A + b˜Hf°,B ˇ˘
are difcult to measure directly.
One method to determine the enthalpy of a reaction is to use can be rarrange to solve for ˜Hf°,C :
Hess’s Law, comparing the fnal and initial states, using standard
˜Hr° + ˝˙a˜Hf°, A + b˜Hf°, B ˆˇ − d ˜Hf°, D
enthalpies of formation of substances. It is also possible to use = ˜Hf°,C
Hess’s Law to determine the standard enthalpy of formation, c
from a measured value for a known reaction involving the sub-
stance, by rearranging Hess’s Law, as shown on the map (and on
the right).
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]
KEY POINTS – INDIRECT METHODS FOR ∆H DETERMINATION
One “indirect” method to fnd ∆H values that cannot be

directly measured is to add several reactions with known CALCULATING AN UNKNOWN ∆H FROM KNOWN VALUES
values of ∆H together in such a way as to produce the ∆Hr • Can calculate as a series of stepwise changes
value sought, which is essentially what Hess’s Law does. Te • ∆H, ∆U are state functions, independent of
boxes on the right (from the map) outline the process used. pathway
18 Example Problems
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.
NaC 2H 3O2 (s) ˜H˜˜

2O
° Na + (aq ) + C 2H 3O2 − (aq ) ˆH soln = − 17.32 kJ
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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ANNALS
OF
THE EARLY CALIPHATE.

CHAPTER I.
ELECTION OF ABU BEKR.
A.H. XI. A.D. 632.
At eventide of a summer day in the

eleventh year of the Hegira, three chief Death of Mahomet, 13 Rabi
I. a.h. XI., June 8, a.d. 632.
‘Companions’ of Mahomet might be seen
issuing in haste from the Great Mosque at Medîna, where, close by
in the chamber of Ayesha, his favourite wife, the Prophet of Arabia
lay dead.[4] They were Abu Bekr, Omar, and Abu Obeida. I will first
describe each briefly, and then explain the object of their errand.
Abu Bekr, now threescore years of
age, was somewhat short in stature, of a Abu Bekr.
spare frame, rounded back, and stooping
gait. His face was thin, complexion smooth and fair, nose aquiline
and sharp, with other features delicate; the forehead high; the eyes
deep-seated and far apart; the veins well marked. His scanty hair
and beard, now for many years white, was dyed red. The
countenance was still in old age handsome; and the expression mild,
but wise and resolute. To him faith in the Prophet had become a
second nature, and, now that his Master was gone, the disciple lived
but to fulfil his will. It was this that nerved a disposition naturally soft
and yielding, and made Abu Bekr, the True,[5] of all the followers of
Mahomet, the firmest and most resolute.
Omar, fifteen years younger, differed
both in frame and temperament. Broad- Omar.
shouldered and tall, he towered above the
crowd. Though somewhat dark in complexion, the face was fresh
and ruddy. He was now bald; and his beard was dyed like his
friend’s. His stride was long, and his presence commanding.
Naturally hasty and passionate, he would twist his moustache when
angry and draw it downwards to his mouth. But time had mellowed
temper; and, beneath an imperious manner, he was bland and
courteous. Their attachment to Mahomet had, on these two friends,
an effect exactly opposite. That which braced the soft nature of Abu
Bekr served to abate the vehemence of Omar. Both stood in a like
relation to the Prophet, each having given a daughter to him in
marriage; Haphsa, Omar’s daughter, was one of Mahomet’s
favourite wives; but Ayesha, the child of Abu Bekr, was queen in his
affections to the end.
On these two men at this moment hung
the future of Islam. The third, who now Abu Obeida.
accompanied them, Abu Obeida, was
between them in age. He was thin, tall, and sinewy; bald, and with
little beard. Mild, unassuming, and unwarlike, he was yet destined to
take a leading part in the conquest of Syria.
It was the afternoon of the day on

which, but an hour or two before, Mahomet Abu Bekr and Omar in the
had breathed his last. The event had come Great Mosque.
unexpectedly at the end. Abu Bekr, thinking the Prophet better, had
shortly before retired to his house in the suburbs of the city. Called
back in haste, he entered Ayesha’s chamber, and kissed the face of
his departed friend, saying:—
‘Sweet wert thou in life; and sweet thou
art in death.’ The mosque was filled with a Men of Medîna would elect a
crowd excited by the voice of Omar, who chief of their own.
wildly proclaimed that the Prophet was not dead, but in a trance; and
that, like Moses, he would surely return to them again. Abu Bekr,
issuing from the chamber (which opened directly from the court of
the mosque), put his friend aside with these memorable words:—
Whoso worshippeth Mahomet, let him know that Mahomet is dead
indeed; but whoso worshippeth God, let him know that God liveth
and dieth not. He added passages from the Corân, in which the
Prophet had said that he would die; and Omar, hearing them as if he
had never heard them before, was speechless. The multitude
quieted down before the solemn words of Abu Bekr. But just then a
messenger hurried up with the report, that the citizens of Medîna—
the Ansâr, had assembled to choose for themselves a chief. The
moment was critical. The unity of the faith was at stake. A divided
power would fall to pieces, and all might be lost. The mantle of the
Prophet must fall upon one successor, and on one alone. The
sovereignty of Islam demanded an undivided Caliphate; and Arabia
would acknowledge no master but from amongst the Coreish. The
die must be cast, and at once.
Such, no doubt, were the thoughts
which occurred to Omar and Abu Bekr on Stormy scene in the hall of
receiving intelligence of the elective the citizens.
conclave; and so, alarmed at the danger, they hastened to the spot,
accompanied by Abu Obeida, if haply they might nip it in the bud. On
the way they met two friendly citizens coming from the assembly,
who warned them of the risk they ran; but, notwithstanding, they
hurried on. The men of Medîna meanwhile, gathered in one of their
rude halls, were bent upon an independent course. ‘We have
sheltered this nest of strangers,’ they cried. ‘It is by our good swords
they have been able to plant the Faith. The Chief of Medîna shall be
from amongst ourselves.’ And they had already fixed their choice on
Sád ibn Obâda, leader of the Beni Khazraj, one of ‘the Twelve’ at
‘the Pledge of Acaba,’ who, sick of a fever, lay covered up at the
further end of the hall. At this moment the three Companions entered
but just in time, for had the Citizens elected Sád and pledged their
troth to him, Medîna might have been irretrievably compromised.
Omar, with his native vehemence, was about to speak, when Abu
Bekr bade him to be silent, and anticipated him, as Omar used in
after days to say, with the same arguments he himself had thought
of, and even better. ‘Every word,’ said Abu Bekr, calmly and firmly,
‘which the Citizens had uttered in their own praise was true, but in
noble birth and influence the Coreish were paramount, and to none
but them would Arabia yield obedience.’ ‘Then,’ cried the men of
Medîna, ‘let there be one chief from amongst you and one from
amongst us.’ ‘Away with you!’ exclaimed Omar; ‘two cannot stand
together’; and even Sád from beneath his covering muttered that to
divide the power would weaken it. High words ensued. Hobâb, on
the side of Sád, cried out, ‘Hear him not! Attend to me, for I am the
well-rubbed Palm-stem.[6] If they refuse, expel them from the city. I
am the Roaring Lion of the desert, and will devour them up.’ ‘The
Lord destroy thee!’ cried Omar; and Hobâb returned the words. The
altercation gaining in heat and bitterness, Abu Bekr saw that it must
be stopped at any risk; so stepping forward he said: ‘Ye see these
two’—and he pointed to Omar and Abu Obeida—‘Choose ye now
whichever of them ye will, and salute him as your Chief.’ ‘Nay,’ cried
both at once, ‘Thou hast already, at the Prophet’s bidding, led the
prayers; thou art our Chief. Stretch forth thine hand.’ He did so, and
they struck their hand on his in token of allegiance.[7] Others began
to follow their example. ‘Wilt thou cut thine own kinsman’s throat?’
cried Hobâb to a Khazrajite about to take the pledge. ‘Not so,’ he
answered; ‘I only yield the right to whom the right is due.’ Whilst they
yet hesitated, the Beni Aus, jealous of the rival tribe and of Sád its
nominee, spake among themselves: ‘If this man be chosen, the rule
will be for ever with the Beni Khazraj. Let us salute Abu Bekr as our
Chief.’[8] The example once set, group
after group advanced to place their hand Abu Bekr elected Caliph.
on that of Abu Bekr, till none was left but Sád, who still lay covered in
the corner. Acknowledged thus by the men of Medîna, there could be
no doubt of Abu Bekr’s acceptance by the Coreish and all the
Refugees.[9] He was one of themselves, and the Prophet, by
appointing him to take his place, when laid aside, at the daily
prayers, had in a manner indicated him as his vicegerent. And so
homage was done on all sides to Abu Bekr. He was saluted as the
‘Caliph,’ or ‘Successor of the Prophet.’
The night was occupied in preparing
the dead for sepulture. The body was Burial of the Prophet.
washed and laid out, and the grave dug in
Ayesha’s apartment, where Mahomet had breathed his last. On the
morrow the citizens, men, women, and children, thronged the
chamber to look once more upon their Prophet’s face. And then the
body was reverently committed to the dust.
The funeral being over, and the court of
the Great Mosque still crowded with the Abu Bekr’s inaugural
mourners, Abu Bekr ascended the pulpit, address.
and, sitting down, was saluted as Caliph by acclamation. Then he
arose, and said: ‘O people! Now I am Chief over you, albeit not the
best amongst you. If I do well, support me; if ill, then set me right.
Follow the true, wherein is faithfulness; eschew the false, wherein is
treachery. The weaker amongst you shall be as the stronger with
me, until that I shall have redressed his wrong; and the stronger shall
be as the weaker, until, if the Lord will, I shall have taken from him
that which he hath wrested. Leave not off to fight in the ways of the
Lord; whosoever leaveth off, him verily shall the Lord abase. Obey
me wherein I obey the Lord and his Prophet; when I disobey, then
obey me not. Now, arise to prayer, and the Lord be with you!’ The
assembly stood up for prayer, and Abu Bekr, for the first time as
Caliph, filled the place of Mahomet.
Besides Sád, there were few, if any,
who refused to do homage to Abu Bekr. Sád declines to swear fealty;
According to most authorities, Aly declined and also (probably) Aly for a
time.
to do so until the death of Fâtima his wife,
six months afterwards. Zobeir and Talha are also mentioned, but
doubtfully.[10] Sád persisted in his refusal; he even threatened to
empty his quiver against the usurpers, and then fight against them
with his retainers. ‘Let him alone,’ was the advice of those around
the Caliph; ‘he is but a single man, and his secession will not signify;
but if force be used against him, then his tribe will fight.’ The advice
approved itself to Abu Bekr’s forbearing spirit. Sád kept aloof, and
never appeared at court or in the mosque. When Omar succeeded to
the Caliphate, he presented himself with these words, ‘I love thee
not, O Omar!’ and, disappearing, eventually died in Syria.
With Mahomet ceased the theocratic
power which, as a prophet, he had The succession, how far
provided for by Mahomet;
exercised; but the kingly functions, as ruler and the precedent now
over all Islam, descended to his successor. established.
According to Arabian notions, such a ruler
was, like the Chieftain of a tribe, the head and representative of the
people, and his nomination was incomplete till confirmed by their
homage. Omar, we are told, in after days declared that the irregular
election of Abu Bekr (referring apparently to the scene enacted in the
hall) should not be drawn into a precedent. It was, he said, an event
the happiest in its consequences for Islam, but justified only by the
urgency of the moment. What might have been the issue if any son
of Mahomet had survived, it is useless to speculate. But certainly the
hereditary descent of kingly power was foreign to the sentiment of
Arabia. As matters stood, Mahomet seems to have shrunk from
anticipating the contingency of his death, and made no preparation
for what should follow. But in so far as we may suppose him to have
felt his illness mortal and his death impending, the nomination of Abu
Bekr to conduct the public prayers (the acknowledged mark of chief
or delegated authority) may be held the natural indication of his wish
that he should succeed.[11] Apart from the counter-claim of the men
of Medîna, there was, in point of fact, neither doubt nor hesitancy in
the election, and the counter-claim died away almost as soon as
made. The notion of divine right, or even of preferential claim, resting
in the Prophet’s family, was the growth of a later age.
CHAPTER II.
EXPEDITION OF OSÂMA TO THE SYRIAN BORDER.
A.H. XI. A.D. 632.
Abu Bekr soon had the opportunity of

showing that he was resolved to carry out Osâma ordered by Mahomet
the commands of Mahomet to the very to lead an expedition against
the Syrian border, a.h. XI.
letter. A few weeks previously an May, a.d. 632.
expedition had been ordered to avenge by
a raid on the Syrian border the disaster which, three years before,
had tarnished the Moslem arms. In that reverse Zeid, the Prophet’s
bosom friend, who led the army, was with many others slain at Mûta;
and the more distinctly now to mark the object of the campaign, his
son Osâma, though still a youth, was nominated by Mahomet to the
command, and bidden to avenge his father’s death. The camp was
formed at Jorf, a little way on the Syrian road; but during the
Prophet’s sickness the force remained inactive, uncertain of the
issue. When the fatal event took place, Osâma broke up the camp,
and carrying back the banner which he had received at the hands of
Mahomet, planted it in the court of the Great Mosque, close by the
door of Ayesha’s apartment.
The day following his inauguration as
Caliph, Abu Bekr took up the banner, and Abu Bekr deaf to
reclamations against its
placing it in the hands of Osâma, in token dispatch.
that he was still commander, bade the
army again assemble and encamp, as it had done before, at Jorf;
and not a man was to be left behind. Obeying the command, the
fighting men of Medîna and its neighbourhood flocked again to the
camp, and even Omar was amongst the number. While yet preparing
to depart, the horizon darkened suddenly. Report of the Prophet’s
mortal illness, followed by tidings of his death, had spread like
wildfire over the land. From every side there now came rumours of
disloyalty, and of the resolve to cast the yoke of Islam off. The sense
of the army, and of Osâma himself, was strongly against leaving the
city thus defenceless, and the Caliph exposed to the risk of sudden
inroad. Omar was deputed to represent this to Abu Bekr, and also to
urge (as had been already urged to Mahomet himself[12]) that, if the
expedition must proceed, some more experienced general should
command. To the first request Abu Bekr replied, calm and unmoved:
‘Were the city swarming round with packs of ravening wolves, and I
left solitary and alone, the force should go; not a word from my
Master’s lips shall fall to the ground.’ At the second demand the
Caliph’s anger kindled: ‘Thy mother be childless, O son of Khattâb!’
he said, seizing Omar by the beard. ‘Shall the Prophet of the Lord
appoint a man to the command, and I, deposing him, appoint
another in his place?’ So Omar returned, without gaining either
object, to the army.
When all was ready for the march, Abu
Bekr repaired to the camp, and He accompanies it a little
way on foot. June, a.d. 682.
accompanied the force a little way on foot,
‘Be mounted,’ said Osâma to him; ‘or else I will dismount and walk
by thee.’ ‘Not so,’ replied Abu Bekr; ‘I will not mount; I will walk and
soil my feet, a little moment, in the ways of the Lord. Verily, every
step in the ways of the Lord is equal to the merit of manifold good
works, and wipeth out a multitude of sins.’ After a while he stopped,
and said to Osâma: ‘If it be thy will, give Omar leave that he may
return with me to the city, for strength and counsel.’ So he gave him
leave.[13]
The army then halted, to receive the
parting injunctions of the Caliph. ‘See,’ said And gives Osâma
he, addressing Osâma, ‘that thou avoid instructions.
treachery and deceit. Depart not in any wise from the right. Thou
shalt mutilate none; neither shalt thou kill child or aged man, nor any
woman. Injure not the date-palm, neither burn it with fire; and cut not
down any tree wherein is food for man or beast. Slay not of the
flocks or herds or camels, saving for needful sustenance. Ye may eat
of the meat which the men of the land shall bring unto you in their
vessels, making mention thereon of the name of the Lord. And the
monks with shaven heads that spend their lives in monasteries, if
they submit, leave them in their cloisters unmolested. Now march
forward in the name of the Lord, and may He protect you from sword
and pestilence!’
So Abu Bekr returned with Omar to
Medîna. Osâma marched by Wâdi al Cora, Osâma returns victorious,
July and August.
in the direction of Dûma, Obna, and the
highlands south of Syria. The brunt of his attack fell upon the Beni
Codhâa, and the semi-Christian tribes which, under the Roman
banner, had discomfited and slain his father. That disaster was now
avenged in fire and blood. The land was ravaged far and near, and
after an absence of two months, the army returned laden with spoil.
[14]
Meanwhile stirring events had transpired at Medîna, of which an

account is given in the chapter following.
CHAPTER III.
MEDINA THREATENED.
A.H. XI. June and July, A.H. 632.
In after days Abu Bekr used to look

back with a just pride and satisfaction to Beneficial effects of Osâma’s
his despatch, against a universal expedition.
reclamation, of Osâma’s force. Public opinion was not long in
justifying the act and attributing thereto results of essential benefit.
The firmness of his attitude inspired the Bedouin tribes with a sense
of stability in the government. If the leaders at Medîna had not been
confident in their strength at home they would not have sent away
this army; and the Arabs, reasoning thus, were restrained from much
that they might otherwise have attempted. Still the position was
critical, and at times sufficiently alarming.
It was indeed a thing of which the brave
old Caliph might proud. ‘The Arabs,’ so the Courageous attitude of Abu
tradition runs, ‘were on all sides rising in Bekr.
rebellion. Apostasy and disaffection began to raise their heads;
Christians and Jews to stretch out their necks; and the Faithful were
left like a flock of sheep without a shepherd—their Prophet gone,
their numbers few, and their foes a multitude.’ It was in face of all this
that Abu Bekr sent off beyond recall his only force, and left Medîna
open and, to the outward eye, defenceless.
During the lifetime of Mahomet three
rivals had already laid claim to the Insurrection throughout
Arabia.
prophetic office and raised the standard of
rebellion. In the south, insurrection had hardly been quelled by the
assassination of the ‘Veiled Prophet’ of Yemen, when tidings of the
death of Mahomet made it burst forth with redoubled violence.
Enshrined in the very centre of the peninsula, Moseilama had
detached the powerful tribes around Yemâma from their allegiance;
and to the north-east, nearer home, Toleiha, the third pretender, was
now openly and dangerously hostile.[15] From every quarter, in rapid
succession, came the news of spreading disaffection. The legates of
Mahomet, the collectors of tithes—all, in fact, who represented the
authority of Islam—fled or were expelled. The Faithful were
massacred, and some confessors suffered a cruel death. Mecca and
Tâyif quivered and vacillated at the first intelligence of the Prophet’s
decease; in the end, through the strong influence of the Coreish,
they stood firm; but they were almost alone. Here and there some
few tribes, under loyal, or, it might be, temporising, chiefs,
maintained the semblance of obedience; but they were hardly
discernible amidst the seething mass of rebellion. Amru, hurrying
back from Omân (whither he had been sent by Mahomet as
ambassador at the Farewell Pilgrimage), witnessed the whole of
Central Arabia either in open revolt or ready to break away on the
first demand of tithes, and his report filled the citizens of Medîna with
dismay.[16] In truth, Islam had never taken firm hold of the distant
provinces; and as for the Bedouins, Mahomet had himself had
frequent cause to chide their fickleness. It was fear of punishment,
and the lust of plunder, rather than attachment to the faith, which had
hitherto held these wild sons of the desert in bondage to the Prophet.
The restraints and obligations of Islam were irksome and distasteful;
and now, on Mahomet’s death well rid of them, they hoped to return
to their lawless life.
As report after report came in of fresh
defection, Abu Bekr could but instruct his Demand for exemption from
tithes refused by Abu Bekr.
officers to hold on where they were able
with the loyal few, hoping to tide over the crisis till the return of
Osâma’s force. For the immediate defence of Medîna he took such
measures as were possible. He called in all that remained of the
faithful tribes in the neighbourhood, and posted pickets at the various
approaches to the city. The turbulent tribes in the near desert to the
east were the first to assume a threatening attitude. The Beni Abs
and Dzobiân massed there in such numbers ‘that the land was
straitened by them,’ and they parted into two bodies, one at
Rabadza,[17] the other at Dzul Cassa, the first station from Medîna
on the road to Nejd. The false prophet Toleiha sent his brother with
men to help them; but they still vacillated between the claims of the
pretender and Islam. At last they bethought themselves of a
compromise. They sent a deputation to Abu Bekr, offering to hold by
Islam and its ritual if only they were excused the tithe. The strangers
bearing the message were welcomed by the chiefs of Medîna, but by
the Caliph their advances were indignantly rejected. He would relax
not a tittle of the legal dues. ‘If ye withhold but the tether of a tithed
camel,’ said Abu Bekr, bluntly, ‘I will fight with you for the same.’ With
this refusal they retired, and also with the intelligence that the city
had but few defenders left. Now was the time, before the army came
back, not only for plunder, but to deliver a decisive blow. Abu Bekr,
foreseeing this, redoubled his precautions. He strengthened the
pickets, and set over them the chief men who had remained with him
—Aly, Zobeir, Talha, and Abdallah ibn Masûd. For the rest of the
people he appointed the Great Mosque a rendezvous. ‘The land hath
rebelled against us,’ he said, ‘and they have spied out our
nakedness and the weakness of our defence. Ye know not whether
they will come upon you by night or come upon you by day, or which
of you may be first attacked. They verily hoped that we should have
accepted their offer, but we rejected it. Wherefore be vigilant and
ready.’
And so it came to pass. They tarried
but three days, when a surprise was Attack on Medîna repelled.
attempted from Dzul Cassa. The outposts
were on the alert, and kept the assailants at bay while the main
guard was hurried up from the Mosque on camels. The Bedouins,
hardly prepared for so warm a reception, fled back upon their
reserves. They were pursued; but the camels of the Moslems, being
used only to draw water for the fields, took fright at a stratagem of
the enemy, and turning, fled back to the Mosque.[18] There were no
casualties among the Medîna troops, but the rebels were
emboldened by the flight of their opponents. Abu Bekr, anticipating a
renewed attack, called out every man capable of bearing arms, and
spent the night in marshalling his force. Next morning, while yet dark,
the Caliph himself led out the little band in regular array, with a
centre and two wings.[19] The enemy were taken by surprise at early
dawn, and as the sun rose were already in full flight. Abu Bekr drove
them with slaughter out of Dzul Cassa, and, leaving a portion of his
little force as an outpost there, returned with the rest to Medîna.
The affair was comparatively small, but
its effect great. As failure would have been Good effect of the victory.
disastrous, perhaps fatal, to Islam, so
victory was the turning-point in its favour. The power of the Prophet’s
successor, even without his proper army, to secure the city and beat
off his assailants was noised abroad. And soon after, the spirits of
the Moslems rose as they saw certain chiefs appear, bringing in the
tithes. The tribes they represented, to be sure, were few in contrast
with the apostate hordes; but it was an augury of brighter days to
come. Safwân and Zibricân, chiefs of two branches of the Beni
Temîm, and Adi son of Hâtim from a loyal branch of the Beni Tay,
were the first to present their legal offerings to the Caliph. Each was
ushered into his presence as an ambassador. ‘Nay,’ said Abu Bekr;
‘they are more than that; they are Messengers of glad tidings, true
men, and defenders of the faith.’ And the people answered, ‘Even
so; now the good things that thou didst promise are appearing.’
Tradition delights to ascribe with pious
gratitude the preservation of Islam to the Saving of Islam due to Abu
aged Caliph’s faith and fortitude. ‘On the Bekr.
death of Mahomet,’ we are told, ‘it wanted but little, and the faithful
had utterly perished. But the Lord strengthened the heart of Abu
Bekr, and stablished us thereby in the resolve to give place, no not
for one moment, to the apostates; and to say but these three words
—Submission, Exile, or the Sword.’ It was the simple faith in
Mahomet of Abu Bekr which fitted him for the task, and made him
carry out the law of his Master to the very letter. But for him, Islam
would have melted away in compromise with the Bedouin tribes, or
might have perished in the throes of its birth.
CHAPTER IV.
RETURN OF OSÂMA. EXPEDITIONS FORMED AGAINST THE
APOSTATE TRIBES THROUGHOUT ARABIA.
A.H. XI. Sept.—Oct. A.D. 632
Osâma at last appeared, and Medîna,

for two months left unprotected, was Osâma’s return. Jumâd II.
relieved from further danger. The army a.h. XI. Sept. a.d. 632.
returned laden with booty. The royal Fifth was delivered to the
Caliph, and by him distributed among the people.[20]
Abu Bekr lost no time in now following
up the advantage he had gained over the Expedition against Beni Abs
and Dzobiân.
Beni Abs and Dzobiân. Driven back from
Dzul Cassa, they had retired to Rabadza, and vented their anger in
destroying by cruel deaths the faithful followers of the Prophet still
left amongst them. Deeply moved at the fate of these confessors,
Abu Bekr took a solemn oath that ‘he would by the like deaths
destroy as many of them as they had slain, or even more.’
Putting Osâma in command of the city,
and leaving the army there for a little while Abu Bekr chastises the rebel
tribes at Rabadza.
to recruit, Abu Bekr took the remaining
force and marched again towards Rabadza. The chief men
expostulated with him on going forth to fight in person. If a
commander were killed in action, his place could easily be filled; but
if the Caliph fell, their head and ruler would be gone. ‘Nay,’ replied
Abu Bekr; ‘but I will go forth, and will be your comrade even as one
of your own selves.’[21] So they marched on, and coming up with the
enemy at Abrac, completely discomfited them, killing some, and
taking others prisoners. The Beni Abs and Dzobiân fled to Toleiha,
and joined his army at Bozâkha. Thereupon Abu Bekr confiscated
their pasture-lands, and declared them to be for ever a public
domain reserved for the stud and camels of the State. On eventually
submitting, they found themselves thus debarred from re-entry; but
this was of comparatively little consequence, as they had, in the end,
ample compensation in the conquered lands beyond Arabia. After
some days spent at Rabadza, the Caliph returned to Medîna.
The army by this time was refitted. The
tithes had begun to come in from many Islam must be reimposed on
neighbouring tribes in token of submission. all Arabia.
Medîna was no longer in peril, and the citizens breathed freely. But a
heavy burden still lay upon the Caliph. Islam was to be the faith of all
Arabia;—‘Throughout the peninsula there shall be no second creed,’
was the behest of Mahomet on his death-bed. False prophets must
be crushed; rebels vanquished; apostates reclaimed or
exterminated; and the supremacy vindicated of Islam. It was, in
short, the mission of Abu Bekr to redeem the dying Prophet’s words.
With this great purpose, Abu Bekr went
forth a second time to Dzul Cassa, and Eleven expeditions
there summoned the whole available despatchedof Arabia.
to different parts
forces of Islam and all the loyal chiefs

around him. He divided them into eleven independent columns, and
over every one appointed a distinguished leader, to whom (following
the example of his Master) he presented a banner. Arabia was
mapped out, and each detachment given a province to reclaim, with
marching orders, where to begin and what course to take. Thus
Khâlid ibn Saîd was named for the Syrian border; Khâlid ibn Welîd
was to subdue Toleiha; and Ikrima with Shorahbîl, Moseilama;
Mohâjir was sent to Yemen; Alâ to Bahrein; Hodzeifa and Arfaja to
Mâhra; and Amru against the Beni Codhâa. And so by this great
scheme, in course of time, no spot would be left unconquered. The
troops retained at home were few; for few were needed now.[22]
Having despatched the various
expeditions, Abu Bekr returned to Medîna. Proclamation summoning
apostates to repent. Oct.,
There his first concern was to publish a a.d. 632.
summons to the apostate tribes,
commanding them everywhere to repent and submit themselves, on
which condition they should be pardoned, and received back into
Islam. Such as refused would be attacked, their fighting men cut to
pieces, and their women and children taken captive. This summons
was sent by the hand of envoys to every province and rebellious
tribe. The Adzân, or call to prayer, was to be the test of faith; if that
were heard and responded to, good and well; if not, the people were
apostate, and as such to be attacked.
Abu Bekr never again left Medîna to
lead his troops. Some say that afterwards Abu Bekr did not again go
he regretted this; but it is not likely that he out to fight.
did so. Medîna, where he continued to reside, was his proper place.
From it, as a central point, he was able to direct the movement of his
commanders all over the peninsula; and with operations in so many
different quarters to control he could not have been better situated.
It is more open to remark that none of
the more distinguished Companions of the No chief ‘Companion’
Prophet were appointed to commands. appointed to a command.
The same was the case with Omar, who was known to say that he
purposely refrained from nominating them to any government, both
out of respect to their dignity,[23] and also to strengthen his own
hands by having them about him as advisers. This latter reason may
also well have weighed with Abu Bekr, who used to take counsel on
all important matters with the leading Companions. Still, it is singular
that men like Aly and Zobeir, who took so prominent a part in the
battles of Mahomet, should now altogether disappear from
operations in the field.

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Thermodynamics Problem Solving in

Physical Chemistry Study Guide and

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Physical chemistry thermodynamics statistical mechanics

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Preface ........................................................................................................................................................................................................................................................................... vii

PART 1: Gases and Gas Laws ................................................................................................................................................3

PART 3: Second and Third Law of Thermodynamics, ∆S ................................................................................................25

Key Points – ∆G and Two-Component Liquid Mixtures..................................................................................................................................50

PART 6: Free Energy, Equilibrium Constants, and Electromotive Force .......................................................................77

Answers to Example Problems..........................................................................................................................................95

Index .................................................................................................................................................................................. 127

◾ Te compressibility factor, Z, is a useful parameter with which to determine when a gas

Z < 1.0 The gas is not acting ideally and Gas A

LAW OF CORRESPONDING STATES

B) Cylinders of compressed O2 gas are typically filled to a pressure of 200 bar

KEY POINTS – MIXTURES OF GASES

1.27 Suppose the apparatus on the right contains

◾ Internal energy, U, is a state function

2.1 Te diagram on the right represents a

In adiabatic processes, there

B) Adiabatically and reversibly?

KEY POINTS – CALORIMETRY

Calorimeters, whether open (constant P) systems or closed (constant V) systems,

CaO(s) + H 2O(l) ° Ca (OH )2 (s)

KEY POINTS – HESS’S LAW CALCULATION FOR ∆H HESS’S LAW

KEY POINTS – INDIRECT METHODS FOR ∆H DETERMINATION

One “indirect” method to fnd ∆H values that cannot be

NaC 2H 3O2 (s) ˜H˜˜

THE EARLY CALIPHATE.

A.H. XI. A.D. 632.

At eventide of a summer day in the

It was the afternoon of the day on

A.H. XI. A.D. 632.

Abu Bekr soon had the opportunity of

Meanwhile stirring events had transpired at Medîna, of which an

A.H. XI. June and July, A.H. 632.

In after days Abu Bekr used to look

A.H. XI. Sept.—Oct. A.D. 632

Osâma at last appeared, and Medîna,

forces of Islam and all the loyal chiefs

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