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Chapter 6
Chapter Six
Energy and Chemical Change
Practice Exercises
æ 1 kcal öæ 1000 cal öæ 4.184 J ö
6.1 J = 140 Cal ç ÷ç ÷ç ÷ = 5.86  105 J = 5.9  105 J
è 1 Cal øè 1 kcal øè 1 cal ø
æ 1 kJ ö
5.9  105 J ç ÷ = 590 kJ
è 1000 J ø
æ 1 kcal ö
6.2 kcal = 160 Cal ç ÷ = 160 kcal
è 1 Cal ø
æ 1000 cal ö
cal = 160 Cal ç ÷ = 1.6  105 cal
è 1 Cal ø
æ 4.184 kJ ö
kJ = 160 Cal ç ÷ = 670 kJ
è 1 Cal ø
æ 4.184 kJ ö æ 1000 J ö
J = 160 Cal ç ÷ç ÷ = 6.7  105 J
è 1 Cal ø è 1 kJ ø
6.3 T = Tfinal – Tinitial = 32 °C – 25 °C = 7 °C

6.4 Twater = Tfinal – Tinitial = 30.0 °C – 20.0 °C = 10.0 °C
æ J ö
qwater = (10.0 °C)(250 g H2O) ç 4.184 ÷ = 10,460 J
è g °C ø
qball bearing = –qwater = –10,460 J
qball bearing –10,460 J
C= = = 55.1 J °C–1
DTball bearing 30.0 °C – 220 °C
6.5 The amount of heat transferred into the water is:

J = (255 g H2O)(4.184 J g–1 °C–1)(30.0 °C – 25.0 °C) = 5330 J
 1 kJ 
kJ =(5330 J)   = 5.33 kJ
 1000 J 
 1 cal 
cal = (5335 J)   = 1280 cal
 4.184 J 
 1 kcal 
kcal = (1280 cal)   = 1.28 kcal
 1000 cal 
6.6 q = mst
549 J = (7.54 g Si)(0.705 J g–1 °C–1)(t°Cf – 25.0 °C)
t°Cf = 128 °C
6.7 The reaction of hydrogen and oxygen is an explosion, as stated, explosions are exothermic
because they release heat.
6.8 Since the container becomes cold, the reaction is absorbing heat, and is endothermic.
6-1
Chapter 6
6.9 Both reactions are exothermic, as stated. The first reaction releases some of the energy as work,
the second reaction releases all of the energy as heat since it is run at constant volume. The
second run releases more heat.
6.10 The first reaction releases some of the energy as work. The second reaction releases all of the
energy as heat. The second reaction will have a larger increase in temperature.
æ 1 mol ö
6.11 mol = (2.85 g) ç ÷ = 0.0233 mol benzoic acid
è 122.12 g ø
qbenzoic acid = Hcombustion  nbenzoic acid = (–3227 kJ mol–1)(0.0233 mol) = –75.3 kJ
qbenzoic acid = –qcalorimeter –qcalorimeter = 75.3 kJ
–qcalorimeter = Ct
75.3 kJ = C( 29.19 °C – 24.05 °C)
75.3 kJ 75.3 kJ
C= = = 14.6 kJ °C–1
29.19 °C – 24.05 °C 5.14 °C
6.12 C12H22O11 MM = (12 mol C  12.01 g/mol C) + (22 mol H  1.01 g/mol H)
+ (11 mol O  16.0 g/mol O) = 342.34 g/mol C12H22O11
qcalorimeter = Ct = 8.930 kJ/°C(26.77 °C – 24.00 °C) = 8.930 kJ/°C(2.77 °C) = 24.74 kJ
qsucrose = –qcalorimeter = –(24.74 kJ) = –24.74 kJ
æ –24.7 kJ ö æ 342.3 g C H O ö
12 22 11 = –5636 kJ mol–1
heat released by 1 mole of sucrose = ç ÷ç ÷
è 1.50 g C12 H 22O 11 ø è 1 mol C12 H 22O 11 ø
= –5640kJ mol–1
æ 1 mol C12 H 22O 11 ö æ 1 Cal ö
heat released by 1 g of sucrose in Cal = –5640 kJ mol–1 ç ÷ç ÷
è 342.3 g C12 H 22O 11 ø è 4.184 kJ ø
= –3.94 Cal/g
6.13 HCl and NaOH react 1:1, therefore the heat released per mole of NaOH will be the same as per
mole of HCl, or –58 kJ mol–1 NaOH
6.14 Net ionic equation: HC2H3O2 + OH– ¾¾® H2O + C2H3O2–

Density of acid solution: 1.00 g/mL
æ 1.00 g ö
Mass of acid solution: 50.00 mL ç ÷ = 50.0 g
è 1.00 mL ø
Mass of base solution: 53.0 g
Total mass = 50 g + 53 g = 103 g solution
qwater = mst = (103 g)(4.184 J g–1 °C–1)(6.6 °C) = 2840 J = 2.84 kJ = 2.8 kJ
qwater = –qreaction
–qreaction = –2.8 kJ
æ 1.00 M ö
mol HC2H3O2 = 50 mL solution ç ÷ = 5.0  10–2 mol HC2H3O2
è 1000 mL ø
–2.84 kJ
NaOH and HC2H3O2 react 1:1, the H° is = –57 kJ/mol HC2H3O2
–2
5.0 ´ 10 mol HC2 H 3O2
One mole of the acid reacts in the reaction, so the H° = –57 kJ
6-2
Chapter 6
6.15 Multiply the reaction and the H° by 3:

3CH4(g) + 6O2(g) ¾¾ ® 3CO2(g) + 6H2O(l) H = –890.5  3 = –2672 kJ
6.16 From the text we are give the thermochemical equation for the formation of 2 moles of NH3:
N2(g) + 3H2(g) ¾¾ ® 2NH3(g) ΔH° = –92.38 kJ
We can proceed by dividing both the equation and the value for ΔH° by 2 and then multiplying
that by 2.5:
1 N2(g) + 3 H2(g) ¾¾ ® NH3 (g) H = –46.29 kJ
2 2
2.5 N2(g)
2
+ 7.5 H2(g)
2
¾¾
® 2.5NH3(g) H = –115.5 kJ
6.17
2 Cu(s) + O 2(g)
-169 kJ
-310 kJ
Cu 2O(s) + 1/2 O 2(g)
-141 kJ
2 CuO(s)
The reaction is exothermic.
6.18
NO(g) + 1/2O2(g)
-56.6 kJ
+90.4 kJ
NO2(g)
+33.8 kJ
1/2N2(g) + O2 (g)
The reaction is endothermic.
6.19 For this problem: divide the second reaction by two:
1 {2N O(g) + 3O (g)
2 2 2 ¾¾ ® 4NO2(g)} H = 12 (–28.0 kJ)
N2O(g) + 3
2
O2(g) ¾¾
® 2NO2(g)} H = –14.0 kJ
Reverse the first reaction
2NO2(g) ¾¾ ® 2NO(g) + O2(g) H = +113.2 kJ
Add the reactions together:
N2O(g) + 32 O2(g) ¾¾ ® 2NO2(g) H = –14.0 kJ
2NO2(g) ¾¾
® 2NO(g) + O2(g) H = +113.2 kJ
N2O(g) + 1
2
O2(g) ¾¾
® 2NO(g) H = +99.2 kJ
6-3
Chapter 6
6.20 This problem requires that we add the reverse of the second equation (remembering to change the
sign of the associated H value) to the first equation:
C2H4(g) + 3O2(g) ¾¾ ® 2CO2(g) + 2H2O(l) H° = –1411.1 kJ
2CO2(g) + 3H2O(l) ¾¾ ® C2H5OH(l) + 3O2(g) H° = +1367.1 kJ
C2H4(g) + H2O(l) ¾¾
® C2H5OH(l) H° = –44.0 kJ
æ 1 moles C3H 6O ö æ -1790.4 kJ/mol ö
6.21 kJ = (12.5 g C3H6O) ç ÷ç ÷ = –385 kJ
è 58.077 g C 3H 6O ø è 1 moles C8H18 ø
It is customary to include the minus sign to indicate that heat is given off (produced) by the
chemical reaction.
æ –5450.5 kJ/mol ö
÷ = –2.62 × 10 kJ
6
6.22 kJ = (480 mol C8H18) ç
è 1 moles C8 18 ø
H
It is customary to include the minus sign to indicate that heat is given off (produced) by the
chemical reaction.
6.23 K(s) + 1
2
Br2(l) ¾¾
® KBr(s) DH fo = –393.8 kJ
6.24 Na(s) + 1
2
H2(g) + C(s) + 3
2
O2(g) ¾¾
® NaHCO3(s) DH fo = –947.7 kJ/mol
6.25 H° = [sum DH fo products] – [sum DH fo reactants]

H° = { DH fo [CaSO4(s)] + 2 DH fo [HCl(g)]} – { DH fo [CaCl2(s)] + DH fo [H2SO4(l)]}
H° = {[1 mol × (–1432.7 kJ/mol)] + [2 mol × (–92.30 kJ/mol)]} –
{[1 mol × (–795.0 kJ/mol)] + [1 mol × (–811.32 kJ/mol)]}
H° = –10.98 kJ = 11.0 kJ
6.26 S(s) + 3
2
O2(g) ¾¾
® SO3(g) DH fo = –395.2 kJ/mol
S(s) + O2(g) ¾¾ ® SO2(g) DH fo = –296.9 kJ/mol
Reverse the first reaction and add the two reactions together to get
SO3(g) ¾¾
® SO2(g) + 1
2
O2(g) DH fo = +98.3 kJ
H° = [sum DH fo products] – [sum DH fo reactants]
H° = {[1 mol SO2 × DH fo SO2(g)] + [ 12 mol O2 × DH fo O2(g)]} – {1 mol SO3 × DH fo SO3(s)}
H° = {[1 mol × (–296.9 kJ/mol)] + [ 12 mol × 0 kJ/mol]} – [1 mol × (–395.2 kJ/mol)]
H° = +98.3 kJ
The answers for the enthalpy of reaction are the same using either method.
6.27 H° = [sum DH fo products] – [sum DH fo reactants]

(a) H° = {2 mol NO2 × DH fo NO2(g)}
– {[2 mole NO × DH fo NO(g)] + [1 mol O2 × DH fo O2(g)]}
= {2 mol × 33.8 kJ/mol} – {[2 mol × 90.37 kJ/mol] + [1 mol × 0 kJ/mol]}
= –113.1 kJ
(b) H° = {[1 mol H2O × DH fo H2O(l)] + [1 mole NaCl × DH fo NaCl(s)]}
6-4
Chapter 6
– {[1 mol NaOH × DH fo NaOH(s)] + [1 mole HCl × DH fo HCl(g)]}

= [(–285.9 kJ/mol) + (–411.0 kJ/mol)] – [(–426.8 kJ/mol) + (–92.30 kJ/mol)]
= –177.8 kJ
Review Questions
6.1 (a) Energy is something that matter possesses by virtue of an ability to do work.
(b) Kinetic energy is the energy of motion.
(c) Potential energy is stored energy.
6.2 Energy can be considered the sum of potential energy and kinetic energy.
1
6.3 Kinetic energy = mv2 where m is the mass of the object and v is its velocity. Since velocity, v,
2
is squared, it has a larger effect on kinetic energy when it is doubled.
6.4 The law of conservation of energy states that the energy of the universe is constant: it can be
neither created nor destroyed but only transferred and transformed. The energy of the child on a
swing is all potential energy when she is at the top of the arc. As she descends, the energy is
converted to kinetic energy. At the bottom at the arc, all the energy is kinetic energy. The
potential energy increases as she rises and is completely potential energy at the top of the arc.
6.5 The pendulum starts at the top of the swing, motionless, so all of the energy is potential energy.
As it falls through the arc, the potential energy is converted into kinetic energy, at the bottom of
the arc, the pendulum is moving at its fastest velocity, and all of the energy is kinetic energy.
Then the pendulum rises on the other side of the arc, and the energy is converted back into
potential energy, until, at the top of the arc, it is all potential energy and the pendulum freezes
before it starts the next swing.
6.6 The instant the Slinky is released, all of the energy is potential energy, as the Slinky compresses,
the energy is converted into kinetic energy. As it reaches its maximum compression, the kinetic
energy is converted back into potential energy. When it is at its maximum compression, all of the
energy is potential energy, and then it begins to stretch again and convert the potential energy into
kinetic energy. The difference between the Slinky and pendulum is that the Slinky's motion is
along a line and the pendulum's motion is in an arc, but both are converting potential to kinetic
energy and back again.
6.7 Chemical energy is the potential energy in substances, which changes into other forms of energy
when substances undergo chemical reactions.
6.8 (a) increases
(b) increases
(c) increases
(d) decreases
6.9 The SI unit of energy is a joule (kg m2 s–2).
1
E= (75 kg)(45 m s–2)2 = 76,000 J
2
æ 1 cal ö
cal = (76,000 J) ç ÷ = 18,000 cal
è 4.184 J ø
6-5
Chapter 6
6.10 The heat produced by combustion of gasoline does no useful work. It is expended into the
surroundings.
6.11 Heat is a form of energy that is transferred between objects, and is the molecular kinetic energy
possessed by molecules as a result of the temperature of the sample. Heat is related to the total
kinetic energy of the molecules and temperature is related to the average kinetic energy.
6.12 The internal energy is the sum of the molecular kinetic energy and the potential energy. The
change in internal energy is defined as the difference in internal energy between the energy of the
products and the energy of the reactants.
6.13 (a) Thermal equilibrium is when two objects in contact with each other are at the same
temperature. The molecules in the hot object are moving with more kinetic energy than
the colder object. As heat is transferred from the hot object to the cold one, the atoms in
the hot object slow down and the atoms in the cold speed up until they have the same
average kinetic energy.
(b) The process is the same for the two liquids, except in the mixing of the liquids, the
molecules from the hot liquid are intermingles with the molecules of the cold liquid.
(c) The mixing of two liquids will achieve thermal equilibrium quicker since the molecules
themselves are mixing.
6.14 (a) point c
(b) point d
(c) It will increase
(b) The height of the curve at point A will decrease. The maximum of the curve will be lower
and shifted to the right.
6.15 a, b, c
6.16 The quart of boiling water has more heat and will cause a more severe burn because the quart has
more water, so that the quart has more kinetic energy.
6.17 The first diagram represents an isolated system. Isolated systems cannot transfer mass or energy
across its boundary.
The second diagram represents an open system. Open systems transfer mass and energy across
boundaries.
The third diagram represents a closed system. Closed systems cannot transfer mass but can
transfer energy across its boundary.
6.18 A state function is a quantity whose value depends only on the initial and final states of the
system and not on the path taken by the system to get from the initial to the final state. Examples
of a state function are pressure, volume, temperature, enthalpy, and energy.
6.19 To determine if an experimental parameter is a state function, conduct the experiment using a
different route between the initial and the final states and see if the difference between the initial
and final states are the same.
6.20 The state of a system in chemistry is usually specified by its current conditions such as its
chemical composition, its pressure, its temperature and its volume.
6.21 The system is that part of the universe under study and separated from the surroundings by a real
or an imaginary boundary. The surroundings are that part of the universe other than the system
6-6
Chapter 6
being studied and separated from the system by a real or an imaginary boundary. An isolated
system does not allow matter or energy to be transferred between the system and the
surroundings. The closed system can absorb or release energy but not mass across the boundary
between the system and its surrounding.
6.22 (a) specific heat
(b) molar heat capacity
(c) heat capacity
(d) energy or heat
6.23 The amount of energy needed to increase the temperature of a substance depends directly on the
specific heat of the substance. So the material with the large specific heat requires the higher
energy input for the 5 C rise in temperature.
6.24 Heat capacity is an extensive property and is proportional to the mass of the sample. Specific heat
is an intensive property.
6.25 A negative value for heat means that heat is released from the system; it is exothermic.
6.26 If object A has twice the specific heat and twice the mass of object B, and the same amount of
heat is applied to both objects, the temperature change of A will be one-fourth the temperature
change in B.
qB = mBsBt
q = amount of heat applied
sB = specific heat of B specific heat of A = 2sB
mB = mass of B mass of A = 2mB
q q 1æ q ö 1
tB = tA = = çç ÷÷ = Dt B
mB s B 2mB ´ 2sB 4 è mB sB ø 4
6.27 (a) Kinetic energy must increase.

(b) The temperature of the system must increase because kinetic energy increased.
6.28 Exothermic; chemical energy decreases; q is negative.
6.29 Endothermic; chemical energy increases; q is positive.
6.30 The potential energy of gasoline and oxygen is higher than the potential energy of carbon dioxide
and water vapor since energy is released as heat in the reaction.
6.31 ∆E = q + w
The change in internal energy is the sum of the heat absorbed by the system and the work done on
it by the surroundings.
6.32 Heat is the energy that flows from a hot object to a cold object as a result of their difference in
temperature.
6.33 Work is the energy expended in moving an opposing force through some particular distance.
6.34 The amount of heat and work expended in a process depends on the path between the initial and
final states.
6.35 The products are CO2, H2O and heat. The heat measured is E since the volume did not change.
6.36 H = E + PV
6-7
Chapter 6
For this reaction, V is approximately zero since the moles of gas for the products equals the
moles of gas for the reactants, so H = E.
6.37 H = E + PV
6.38 H > 0 for an endothermic change.
6.39 The enthalpy of the surroundings must decrease by 100 kJ, since energy is conserved.
6.40 w = –PV
6.41 Since the heats of reaction will in general depend on temperature and pressure, we need some
standard set of values for temperature and pressure so that comparisons of various heats of
reaction are made under identical conditions. The standard temperature is 25 °C, slightly above
room temperature, and the standard pressure is 1 atmosphere.
6.42 A thermochemical equation contains the value for the associated H.
6.43 Fractional coefficients are permitted because thermochemical properties are extensive (they
depend on the amount of material present). If 1/2 the amount of materials reacts, 1/2 the amount
of heat will be generated or required. The coefficients of thermochemical equations are moles of
substance.
6.44 H is a state function.
6.45 The reaction must (1) produce one mole of a compound at 25 C and 1 atm, and (2) the reactants
must be elements in their standard states.
6.46 (a) The standard enthalpy of reaction, DH fo , changes sign.

(b) DH fo is multiplied by three.
(c) DH fo is divided by two.
6.47 The heat of formation thermochemical equations for H2O(g) and CO2(g).
6.48 The heat of formation thermochemical equations for H2O(g), CO2(g), SO2(g), and NO2(g).
Review Problems
1 2 1 1
6.49 KE = mv KE1 = m(30 mi/h)2 KE2 = m(60 mi/h)2
2 2 2
1 1
KE1 = m(900 mi2/h2) KE2 = m(3600 mi2/h2)
2 2
KE 2 3600
= =4
KE1 900
There is a four-fold increase in the kinetic energy due to the doubling of the speed of the car.
If the speed decreases to 10 mph:
1 1
KE1 = m(10 mi/h)2 KE2 = m(30 mi/h)2
2 2
1 1
KE1 = m(100 mi2/h2) KE2 = m(900 mi2/h2)
2 2
6-8
Chapter 6
KE2 900
= =9
KE1 100
The kinetic energy decreases by 9 times due to the decreasing of the speed of the car by 10 mph.
1 1
6.50 KE1 = m1v2 m2 = 2m1 KE2 = 2m1v2
2 2
KE 2 2m1
= =2
KE1 m1
There is a two-fold increase in the kinetic energy due to the doubling of the mass of the truck.
The kinetic energy decreases to one-tenth its original kinetic energy when the mass decreases to
one-tenth its original mass.
æ 32.00 g O2 ö æ 1 kg O 2 ö
6.51 kg O2 molecule = 1 mol O2 ç ÷ç ÷
è 1 mol O2 ø è 1000 g O2 ø
= 3.200  10–3 kg
1 2 1
KE = mv = (3.200  10–3 kg)(255 m s–1)2 = 1.04  103 J
2 2
æ 1 kJ ö
1.04  103 J ç ÷ = 1.04 kJ
è 103 J ø
æ 1 mol CCl 4 öæ 153.81 g CCl öæ 1 kg CCl ö

6.52 kg = 1 CCl4 molecule ç ÷ç
ç 1 mol CCl ÷÷çç 1000 g CCl ÷÷
4 4
ç 6.022 ´ 1023 ÷
molecule CCl 4 øè
è 4 øè 4ø
= 2.55  10–25 kg
1 2 1
KE = mv = (2.55  10–25 kg)(255 m s–1)2 = 8.30  10–21 J
2 2
æ 1 aJ ö
8.30  10–21 J ç ÷ = 0.00830 aJ
è 10 –18 J ø
6.53 t = 15.0 C – 25.0 C = –10.0 C

q = ms∆t
é æ 18.02 g H O öù
q = ê1.75 mol H 2O ´ çç 2 ÷ú × 4.184 J g–1 °C–1 × –10.0 C = –1320 J
÷
êë è 1 mol H 2O øúû
 1 cal 
cal = (–1320 J) ×   = –315 cal
 4.184 J 
6.54 q = ms∆t
Assume that the density of water is 1.00 g mL–1 so that the mass of water is the same as its
volume.
q = 215 g × 4.184 J g–1 °C–1 × (99.0 °C – 25.0 °C) = 6.66 × 104 J
 1 cal 
cal = (6.66 × 104 J) ×  4
 = 1.59 × 10 cal
 4.184 J 
6.55 qFe = (85.0 g Fe)(0.4498 J g–1 C–1)(35.0 C – 85.0 C) = –1912 J

qFe = –qH2O = 1912 J
q
m=
sDt
6-9
Chapter 6
æ ö
ç 1912 J ÷
g H2O = ç ÷ = 45.7 g H2O
( -1
ç 4.184 J g °C
è
-1
( )
35.0 °C – 25.0 °C) ÷
ø
6.56 The heat gained by the water must equal the heat lost by the copper. To get the correct signs for
the heat transfer, remember heat lost is negative and heat gained is positive.
qCu = –qH2O q = ms∆t
mCu × 0.387 J g C × (32.3 C – 67.0 C) = –[100.0 g × 4.184 J g–1 C –1 × (32.3 C – 27.0 C)]
–1 o –1
mCu = 165 g of copper

6.57 (a) ∆t = 28.00 °C – 24.00 °C = 4.00 °C
q = ms∆t
qH2O = 4.184 J g–1 °C–1 × 100 g × 4.0 °C = 1.67 × 103 J
(b) 1.67 × 103 J
1.67 ´ 103 J
(c) = 23.2 J °C–1
100 °C – 28.0 °C
–1
23.2 J °C
(d) = 0.464 J g–1 °C–1
50.0 g
6.58 (a) qH2O = 4.184 J g–1 °C–1 × 200.0 g × 1.50 °C = 1.26 × 103 J
(b) 1.26 × 103 J
1.26 ´ 103 J
(c) = 13.5 J °C–1
120.00 °C – 26.50 °C
(d) 1.26 × 103 J = mCu × 0.387 J °C–1 × (120 °C – 26.50 °C)
mCu = 34.8 g
J æ 0.4498 J öæ 55.847 g Fe ö J
6.59 =ç ÷ç ÷ = 25.12
mol °C è g °C øè 1 mol Fe ø mol °C
J æ 0.586 cal öæ 4.184 J öæ 46.08 g C H OH ö

6.60 =ç ÷ç ÷ç 2 5 ÷ = 113 J mol –1 °C–1
mol °C è g °C øè cal øçè 1 mol C2H5OH ÷ø
6.61 4.184 J g–1 °C–1 × (4.54 × 103 g) × (58.65 °C – 60.25 °C) = –3.04 × 104 J = –30.4 kJ
6.62 4.184 J g–1 °C–1 × (2.46 × 103 g) × (27.31 °C – 25.24 °C) = 2.1 × 104 J = 21.3 kJ
6.63 HNO3(aq) + KOH(aq) ¾¾ ® KNO3(aq) + H2O(l)

Keep in mind that the total mass (assume the densities to be 1.00 g/mL for the solutions) must be
considered in this calculation, and that both liquids, once mixed, undergo the same temperature
increase:
qH2O = (4.18 J/g °C) × (55.0 g + 55.0 g) × (31.8 °C – 23.5 °C)
= 3.8 × 103 J of heat energy released
Next determine the number of moles of reactant involved in the reaction:
0.0550 L × 1.3 mol L–1 = 0.072 mol of acid and of base.
qH2O = –qreaction = –3.8 × 103 J
( –3.8 ´ 10 J ) ç 3 æ
1 kJ ö
÷
è 1000 J ø
Thus the enthalpy change is: = - 53 kJ
(0.072 mol) mol
6-10
Chapter 6
6.64 HCHO2(aq) + NaOH(aq) ¾¾ ® NaCHO2(aq) + H2O(l)

Keep in mind that the total mass (assume the densities to be 1.00 g/mL for the solutions) must be
considered in this calculation, and that both liquids, once mixed, undergo the same temperature
increase:
qH2O = (4.18 J/g °C) × (75.0 g + 45.0 g) × (23.4 °C – 22.4 °C)
= 5.02 × 102 J of heat energy released
Next determine the number of moles of reactant involved in the reaction:
0.0750 L × 1.07 mol/L = 0.080 mol of acid
0.0450 L × 1.78 mol/L = 0.080 mol of base.
qH2O = –qreaction = –3.8 × 103 J
( –5.02 ´ 10 J ) ç
2 æ 1 kJ ö
÷
kJ è 1000 J ø
Thus the enthalpy change is: = = –6.3 kJ
mol (0.080 mol) mol
6.65 (a) C3H8(g) + 5O2(g) ¾¾ ® 3CO2(g) + 4H2O(l)

(b) qV = (97.1 kJ/C)(27.282 C – 25.000 C) = 222 kJ = 2.22 × 105 J
(c) H = – 222 kJ/mol
6.66 (a) C7H8(l) + 9O2(g) ¾¾ ® 7CO2(g) + 4H2O(l)
(b) qV = (45.06 kJ/C)(26.413 C – 25.000 C) = 63.67 kJ = 6.367 × 104 J
 6.367  104 J   92.14 g C7 H8 
J = (1 mol C7H8)   = 3.911 × 106 J
  1 mol C7 H8 
(c)
 1.500 g
 
6.67 E = q + w = 28 J – 45 J = –17 J
6.68 E = q + w = 22 J + 48 J = 70 J
6.69 Here, E must = 0 in order for there to be no change in energy for the cycle.
E = q + w
0 = q + (–100 J)
q = +100 J
6.70 E = q + w
= 345 J + 235 J
= 580 J
6.71 If the engine absorbs 250 J of heat, the maximum amount of work it can do is 250 J.
6.72 E = q + w
–535 J = q + (–455 J)
q = –80 J
6.73 (a) Divide the given equation by 4.
NH3(g) + 7/4 O2(g) ¾¾ ® NO2(g) + 3/2H2O(g) H° = –1132 kJ/4 = –283 kJ
(b) Divide the given equation by 6
2/3NH3(g) + 7/6 O2(g) ¾¾ ® 2/3 NO2(g) + H2O(g) H° = –1132 kJ/6 = –189 kJ
6.74 (a) Multiply the given equation by the fraction 2/3.
2CO(g) + O2(g) ¾¾ ® 2CO2(g) H° = –566 kJ
6-11
Chapter 6
(b) To determine H for 1 mol, simply multiply the original H by 1/3; –283 kJ/mol.
æ -1203 kJ öæ 1 mol Mg ö
6.75 q = 6.54 g Mg ç ÷ç ÷ = –162 kJ
è 2 mol Mg øè 24.305 g Mg ø
162 kJ of heat are evolved
æ 1 mol CH OH öæ -1199 kJ ö
6.76 kJ = 46.0 g CH3OH çç 3 ÷÷çç ÷÷ = –861 kJ
è 32.04 g CH3OH øè 2 mol CH 3OH ø
æ 1 mol CH öæ 16.04 g ö
6.77 g CH4 = –432 kJ çç 4 ÷ç ÷÷ = 8.64 g
÷ç
è –802 kJ øè 1 mol CH 4 ø
æ 2 mol CH OH öæ 32.04 g ö
6.78 g CH3OH = –625 kJ çç 3 ÷÷çç ÷÷ = 33.4 g
è -1199 kJ øè 1 mol CH3OH ø
6.79
6.80
NO(g) + 1/2O2(g)
-56.6 kJ
+90.4 kJ
NO2(g)
+33.8 kJ
1/2N2(g) + O2 (g)
The enthalpy change for the reaction NO(g) + 1

2
O2(g) ¾¾
® NO2(g) is –56.6 kJ as seen in the
figure above.
6.81 Since NO2 does not appear in the desired overall reaction, the two steps are to be manipulated in
such a manner so as to remove it by cancellation. Add the second equation to the reverse of the
first, remembering to change the sign of H° for the first equation, since it is to be reversed:
2NO2(g) ¾¾ ® N2O4(g) H° = –57.93 kJ
2NO(g) + O2(g) ¾¾ ® 2NO2(g) H° = –113.14 kJ
Adding, we have:
2NO(g) + O2(g) ¾¾ ® N2O4(g) H° = –171.07 kJ
6-12
Chapter 6
6.82 Reverse the first equation, multiply the result by two, and add it to the second equation:
2KCl(s) + 2H2O(l) ¾¾ ® 2HCl(g) + 2KOH(s), H° = 407.2 kJ
H2SO4(l) + 2KOH(s) ¾¾ ® K2SO4(s) + 2H2O(l), H° = –342.4 kJ
Adding gives us:
2KCl(s) + H2SO4(l) ¾¾ ® 2HCl(g) + K2SO4(s), H° = 64.8 kJ
6.83 If we label the four known thermochemical equations consecutively, 1, 2, 3, and 4, then the sum
is made in the following way: Divide equation #3 by two, and reverse all of the other equations
(#1, #2, and #4), while also dividing each by two:
1 Na O(s) + HCl(g)
2
2 ¾¾ ® 12 H2O(l) + NaCl(s) H° = –253.66 kJ
NaNO2(s) ¾¾
® 1
2
Na2O(s) + 1
2
NO2(g) + 1
2
NO(g) H° = +213.57 kJ
1
2
NO(g) + 1
2
NO2(g) ¾¾
® 1
2
N2O(g) + 1
2
O2(g) H° = –21.34 kJ
1
2
H2O(l) + 1
2
O2(g) + 1
2
N2O(g) ¾¾
® HNO2(l) H° = –17.18 kJ
Adding gives:
HCl(g) + NaNO2(s) ¾¾
® HNO2(l) + NaCl(s), H° = –78.61 kJ
6.84 Reverse the second and the third thermochemical equations and add them to the first:
CaO(s) + 2HCl(aq) ¾¾ ® CaCl2(aq) + H2O(l) H° = –186 kJ
Ca(OH)2(s) ¾¾ ® CaO(s) + H2O(l) H° = 65.1 kJ
Ca(OH)2(aq) ¾¾ ® Ca(OH)2(s) H° = 12.6 kJ
Adding gives:
Ca(OH)2(aq) + 2HCl(aq) ¾¾ ® CaCl2(aq) + 2H2O(l) H° = –108 kJ
6.85 Multiply all of the equations by 1 and add them together.
2
1 CaO(s) + 1 Cl2(g) ¾¾® 12 CaOCl2(s) H = –55.5 kJ
2 2
1
2
H2O(l) + 1 CaOCl (s) + NaBr(s)
2 2 ¾¾® NaCl(s) + 1
2
Ca(OH)2(s) + 1
2
Br2(l) H= –30.1 kJ
1
2
Ca(OH)2(s) ¾¾
® 1
2
CaO(s) + 1
2
H2O(l) H= +32.6 kJ
Adding gives:
1 Cl (g) + NaBr(s)
2 2 ¾¾
® NaCl(s) + 1
2
Br2(l) H= –53 kJ
6.86 The equation we want is Cu(s) + 1

2
O2(g) ¾¾
® CuO(s). If we multiply all reactions by 1
2
and
reverse the second reaction we get:
Cu(s) + 1
2
S(s) ¾¾
® 1
2
Cu2S(s) H = 1
2
(–79.5 kJ)
1
2
SO2(g) ¾¾
® 1
2
S(s) + 1
2
O2(g) H = 1
2
(+297 kJ)
1
2
Cu2S(s) + O2(g) ¾¾
® CuO(s) + 1
2
SO2(g) H = 1
2
(–527.5 kJ)
Adding gives:
Cu(s) + 12 O2(g) ¾¾
® CuO(s) H = –155 kJ
6.87 Multiply the second equation by two and add them together:
3Mg(s) + 2NH3(g) ¾¾ ® Mg3N2(s) + 3H2(g) H = –371 kJ
N2(g) + 3H2(g) ¾¾ ® 2NH3(g) H = 2(–46 kJ)
6-13
Chapter 6
Adding gives:
3Mg(s) + N2(g) ¾¾
® Mg3N2(s) H = –463 kJ
6.88 We need to eliminate the NO2 from the two equations. To do this, multiply the first reaction by 3
and the second reaction by two and add them together.
12NH3(g) + 21O2(g) ¾¾ ® 12NO2(g) + 18H2O(g) H = 3(–1132 kJ)
12NO2(g) + 16NH3(g) ¾¾ ® 14N2(g) + 24H2O(g) H = 2(–2740 kJ)
28NH3(g) + 21O2(g) ¾¾ ® 14N2(g) + 42H2O(g) H = –8876 kJ
Now divide this equation by 7 to get
4NH3(g) + 3O2(g) ¾¾ ® 2N2(g) + 6H2O(g) H = 1/7(–8876 kJ) = –1268 kJ
6.89 The heat of formation is defined as the enthalpy change when one mole of a compound is
produced from its elements in their standard states.
Only (c) satisfies this requirement.
For choice (a,) reactant CO(NH2)2 is not an element
For choice (b), O and H are not the standard states for oxygen and nitrogen gas. The state for C is
not given as graphite or as a solid.
For choice (d), the reaction is not balanced
6.90 The heat of formation is defined as the enthalpy change when one mole of a compound is
produced from its elements in their standard states.
Only (b) satisfies this requirement.
For choices (a) and (c) the reactants are not elements in their standard state; (a) has molecules as
reactants and (c) has atoms.
Choice (d) might look okay but it does not fit the definition that one mole of product is formed.
6.91 (a) 2C(s, graphite) + 2H2(g) + O2(g) ¾¾
® HC2H3O2(l) DH fo = –487.0 kJ
(b) 2C(s, graphite) + 1
2
O2(g) + 3H2(g) ¾¾
® C2H5OH(l) DH fo = –277.63 kJ
(c) Ca(s) + S(s) + 3O2(g) + 2H2(g) ¾¾
® CaSO4·2H2O(s) DH fo = –2021.1 kJ
(d) 2Na(s) + S(s) + 2 O2(g) ¾¾
® Na2SO4(s) DH fo = – 1384.5 kJ
6.92 (a) Mg(s) + Cl2(g) + 2H2(g) + O2(g) ¾¾

® MgCl2·2H2O(s) DH fo = –1280 kJ
(b) N2(g) + 4H2(g) + 2Cr(s) + 7
2
O2(g) ¾¾
® (NH4)2Cr2O7(s) DH fo = –1807 kJ
(c) P(s,white) + 1
2
O2(g) + 3
2
Cl2(g) ¾¾
® POCl3(g) DH fo = –558.5 kJ
6.93 (a) DH o = {[1 mol O2(g)  DH fo O2(g)] + [2 mol H2O(l)  DH fo H2O(l)]}

– {2 mol H2O2(l)  DH fo H2O2(l)}
= 0 kJ/mol + [2 mol × (–285.9 kJ/mol)] – [2 × (–187.6 kJ/mol)]
= –196.6 kJ
(b) DH o = {[1 mol H2O(l) × DH fo H2O(l)] + [1 mol NaCl(s) × DH fo NaCl(s)]}
– {[1 mol HCl(g) × DH fo HCl(g)] + [1 mole NaOH × DH fo NaOH(s)]}
= [1 mol × (–285.9 kJ/mol)] + [1 mol × (–411.0 kJ/mol)]
– [1 mol × (–92.30 kJ/mol)] – [1 mol × (–426.8 kJ/mol)]
= –177.8 kJ
6-14
Chapter 6
6.94 (a) DH fo = {[1 mol HCl(g)  DH fo HCl(g)] + [1 mol CH3Cl(g)  DH fo CH3Cl(g)]}

– {[1 mol CH4(g)  DH fo CH4(g)] + [1 mol Cl2(g)  DH fo Cl2(g)]}
– [1 mol × (–74.848 kJ/mol)] – [1 mol × (0.0 kJ/mol)]
= –99.5 kJ
(b) DH fo = {[1 mol H2O(l)  DH fo H2O(l)] + [1 mol CO(NH2)2(s)  DH fo CO(NH2)2(s)]}
– {[2 mol NH3(g)  DH fo NH3(g)] – [1 mol CO2(g)  DH fo CO2(g)]}
– [2 mol × (–46.19 kJ/mol) – [1 mol × (–393.5 kJ/mol)]
= –133.2 kJ
6.95 C12H22O11(s) + 12O2(g) ¾¾
® 12CO2(g) + 11H2O(l) DH combustion
o
= –5.65 × 103 kJ/mol
DH combustion
o
= [sum Hf products] – [sum Hf reactants]
= {[12 mol CO2(g) × DH fo CO2(g)] + [11 mol H2O(l) × DH fo H2O(l)]}
– {[1 mol C12H22O11(s) × DH fo C12H22O11(s)] + [12 mol O2(g) × DH fo O2(g)]}
Rearranging and realizing the HfO2(g) = 0 we get
DH fo C12H22O11(s) = [12 mol × DH fo CO2(g)] + [11 mol H2O(l) × DH fo H2O(l)] – DH combustion
o
= 12(–393.5 kJ) + 11(–285.9 kJ) – (–5.65 × 103 kJ) = –2.22 × 103 kJ

6.96 DH fo C2H2(g) = 1 {[4 mol CO2(g) × DH o CO2(g]) + [2 mol H2O(l) × DH o H2O(l)]
f f – DHcombustion
o
}
2
= 1 {4(–393.5 kJ) + 2(–285.9 kJ) – (–2599.3 kJ) = +226.8 kJ
2
Additional Exercises
6.97 Water has the highest specific heat and therefore will take the greatest amount of heat to raise its
temperature a given amount.
Lead has the smallest specific heat, though gold is only 0.001 J g–1 °C–1 higher, so it will increase
the most in temperature for the given amount of applied heat.
6.98 HCl(aq) + NaOH(aq) ¾¾ ® NaCl(aq) + H2O(l)
The heat of neutralization is released to three "independent" components of the system, all of
which undergo the same temperature increase: t = 20.610 °C – 16.784 °C = 3.826 °C. Also, the
total heat capacity of the system is the sum of the three heat capacities:
Csystem = CHCl + CNaOH + Ccalorimeter
= (4.031 J g–1 °C–1 × 610.29 g) + (4.046 J g–1 °C–1 × 615.31 g) + 77.99 J °C–1
= 5028 J °C–1
The heat flow to the system is thus:
q = 5028 J °C–1 × 3.826 °C = 1.924 × 104 J = 19.24 kJ
The heat of neutralization is the negative of this value, since this process is exothermic:
qsystem = qreaction
–19.24 kJ
Hneutralization = = –57.98 kJ/mol
0.33183 mol HCl
6-15
Chapter 6
6.99 qgranite = (2000 g)(0.803 J g–1 °C–1)(tfinal – 95 C)

= (1606 J C–1)(tfinal – 95 C)
= (1606 J °C–1)(tfinal) – 152,600 J
æ 1000 mL öæ 1 g öæ 4.184 J ö
qwater = (2.00 L) ç
è 1L
÷ç
øè 1 mL
÷çç
øè g C ø
o
÷t
÷ ( o
final – 22 C )
= (8368 J C–1)(tfinal – 22 C)
= (8368 J °C–1)(tfinal) – 184,100 J
qgranite = –qwater
(1606 J °C–1)(tfinal) – 152,600 J = –[(8368 J °C–1)(tfinal) – 184,100 J]
(1606 J °C–1)(tfinal) – 152,600 J = –(8368 J °C–1)(tfinal) + 184,100 J
336,700 J = (9974 J)(tfinal)
tfinal = 33.8 C
6.100 Multiply the first reaction by 1 :
2
1
2
Fe2O3(s) + 3
2
CO(g) ¾¾
® Fe(s) + 3
2
CO2(g) H° = 1
2
(–28 kJ)
Reverse the second reaction AND multiply by 1/6:
1 Fe O (s) + 1 CO (g)
3 3 4
6 2 ¾¾ ® 12 Fe2O3(s) + 16 CO(g) H° = 1
6
(+59 kJ)
Reverse the third reaction AND multiply by 1/3:
FeO(s) + 13 CO2(g) ¾¾ ® 13 Fe3O4(s) + 13 CO(g) H° = 1
3
(–38 kJ)
Now add the equations together:
FeO(s) + CO(g) ¾¾ ® Fe(s) + CO2(g) H° = –16.8 kJ
6.101 H°reaction = {[1 mol CO2(g) × DH fo CO2(g)] + [1 mole Fe(s) × DH fo Fe(s)]}
– {[1 mol FeO(s) × DH fo FeO(s)] + [1mol CO(g) × DH fo CO(g)]}
Rearranging, and remembering that DH fo Fe(s) = 0
DH fo FeO(s) = DH fo CO2(g)] – DH fo CO(g) – H°reaction
DH fo = –393.5 kJ – (–110.5 kJ) – (–16.8 kJ) = – 266.2 kJ
6.102 H° = {[8 mol CO2(g) × DH fo CO2(g)] + [10 mol H2O(l) × DH fo H2O(l)] + [2 mol N2(g) × DH fo N2(g)]}
– {[4 mol C2H5NO2(s) × DH fo C2H5NO2(s)] + [9 mol O2(g) × DH fo O2(g)]}

The value of H° for the given combustion reaction is:
H° = 4 mol × (–973.49 kJ mol–1) = –3894.0 kJ
The standard enthalpy of formation for each substance is taken from Table 6.2:
–3894.0 kJ = [8 mol × (–393.5 kJ/mol)] + [10 mol × (–285.9 kJ/mol)] – [4 mol × DH fo C2H5NO2]
Solving for the desired enthalpy of formation, we have:
DH fo C2H5NO2 = –528.3 kJ/mol
6.103 The equation may be written as: 1

2
H2(g) + 1
2
Br2(l) ¾¾
® HBr(g) DH fo = –36 kJ
To obtain H, combine the equations in the following manner:
Br2(aq) + 2KCl(aq) ¾¾ ® Cl2(g) + 2KBr(aq) H° = 96.2 kJ
H2(g) + Cl2(g) ¾¾® 2HCl(g) H° = –184 kJ
6-16
Chapter 6
2HCl(aq) + 2KOH(aq) ¾¾ ® 2KCl(aq) + 2H2O(l) H° = –115 kJ

2KBr(aq) + 2H2O(l) ¾¾ ® 2HBr(aq) + 2KOH(aq) H° = 115 kJ
2HCl(g) ¾¾ ® 2HCl(aq) H° = –154 kJ
2HBr(aq) ¾¾ ® 2HBr(g) H° = 160 kJ
Br2(l) ¾¾ ® Br2(aq) H° = –4.2 kJ
Add all of the above to get:
H2(g) + Br2(l) ¾¾ ® 2HBr(g) H° = –86 kJ
Now divide this equation by two to give the thermochemical equation for the formation of 1 mol
of HBr(g):
1 H (g) + 1 Br (l)
2
2
2
2 ¾¾ ® HBr(g); H° = –43 kJ
Comparing this value to the Hf° value listed in Appendix C.2 and at the outset of this problem,
we see that this experimental data indicates a value that is close to the reported value.
6.104 The equation we want is:
2C(s) + H2(g) ¾¾ ® C2H2(g)
Take this one step at a time. Start with the fourth equation:
CaC2(s) + 2H2O(l) ¾¾ ® Ca(OH)2(s) + C2H2(g) H° = –126 kJ
Add the reverse of the first equation and get rid of calcium hydroxide:
Ca(OH)2(s) ¾¾ ® CaO(s) + H2O(l) H° = +65.3 kJ
Add the second equation to eliminate the CaO(s):
CaO(s) + 3C(s) ¾¾ ® CaC2(s) + CO(g) H° = +462.3 kJ
This also eliminates the CaC2(s) we had from the first equation. To eliminate the H2O, reverse the
last equation AND multiply by 1/2:
H2(g) + 1/2O2(g) ¾¾ ® H2O(l) H° = –286 kJ
Now get rid of the CO by reversing the fifth equation AND multiplying by 1 :
2
CO(g) ¾¾
® C(s) + 1 O2(g) H° = +110 kJ
2
Add the equations together to get:
2C(s) + H2(g) ¾¾ ® C2H2(g) H° = 225.6 kJ
6.105 C12H22O11(s) + 12O2(g) ¾¾ ® 12CO2(g) + 11H2O(l)
Hcombustion = [sum DH f products] – [sum DH fo reactants]
o
= {[12 mol CO2(g) × HfCO2(g) + [11 mol H2O(l) × HfH2O(l)]}

– {[1 mol C12H22O11(s) × HfC12H22O11(s)] + [12 mol × HfO2(g)]}
= [12(–393.5 kJ) + 11(–285.9 kJ)] – [(–2230 kJ) + 12(0 kJ)] = –5.64 × 103 kJ/mol
This is the amount of heat liberated for 1 mol of sucrose. Thus, for 28.3 g we have,
æ 1 mol öæ -5640 kJ ö
q = (28.3 g) ç ÷ç ÷ = –466 kJ
è 342.3 g øè 1 mol ø
6.106 1
2
HCHO2(l) + 1
2
H2O(l) ¾¾
® 1
2
CH3OH(l) + 1
2
O2(g) H° = +206kJ
1
2
CO(g) + H2(g) ¾¾
® 12 CH3OH(l) H° = –64 kJ
1
2
HCHO2(l) ¾¾
® 1
2
CO(g) + 1
2
H2O(l) H° = –17 kJ
Add these together:
6-17
Chapter 6
HCHO2(l) + H2(g) ¾¾
® CH3OH(l) + 1
2
O2(g) H° = +125 kJ
6.107 Simply add the two together to get:

O3(g) + O(g) ¾¾ ® 2O2(g) H° = –394 kJ
6.108 Oxygen can absorb UV radiation and form ozone. Then the ozone can absorb the UV radiation
and forms oxygen.
æ 2000 lb öæ 453.6 g öæ 1 kg ö
6.109 K.E. = 1 mv2 = 1 (14.0 tons) ç ÷ç ÷ç ÷
2 2
è 1 ton øè 1 lb øè 1000 g ø
éæ 45.0 mi öæ 1 hr öæ 5280 ft öæ 30.48 cm öæ 1 m öù2
× êç ÷ç ÷ç ÷ç ÷ç ÷ú
êëè hr øè 3600 s øè 1 mi øè 1 ft øè 100 cm øúû
= 2.57 × 106 J = 2.57 × 103 kJ
 3.785 L   1000 mL  1 g 
mwater = (5.00 gal)     = 18900 g water
 1 gal   1 L  1 mL 
Increasing the temperature of water:
2.57 × 106 J = (4.184 J g–1 C–1)(18900 g)(t)
t = 32 C
6.110 The desired reaction is given below:
CO2(g) + 2H2O(l) ¾¾ ® CH4(g) + 2O2(g)
∆Hreaction = {[1 mol CH4(g) × Hf°CH4]} – {[1 mol CO2(g) × Hf°CO2] + [1mol H2O(l) ×
2Hf°H2O(l)]}
= –74.848 kJ mol–1 – [–393.5 kJ mol–1 + (–285.9 kJ mol–1)]
= +890.4 kJ
Since ∆Hreact equals the amount of work needed for this reaction, w = +890.4 kJ.
It is difficult to carry out this reaction as it is a non-spontaneous reaction requiring an input of
energy. However, when energy is input to this mixture it is almost impossible to control what
product will be formed.
6.111 (a)
(b) Water: q < 0 Copper: q > 0

(c) qlost + qgained = 0 Also, we must assume the density of water at these temperatures is 1.00 g
mL–1
[50 g × 4.184 J g–1 °C–1 × (tf – 32.4 °C)] + [7.38 g × 0.387 J g–1 °C–1 × (tf – (–15 °C))] = 0
tf = 31.76 °C = 31.8 °C
6.112 Na2CO3(s) + 2HCl(aq) ¾¾ ® 2Na2+(aq) + 2Cl–(aq) + H2O + CO2(g)
∆Hreact ={[2 mol Na+(aq) × DH fo Na+(aq)] + [2 mol Cl–(aq) × DH fo Cl–)]
6-18
Chapter 6
+ [1 mol CO2 × DH fo CO2] + [1 mol H2O(l) × DH fo H2O(l)]}

– {[1 mol Na2CO3 × DH fo Na2CO3] + [2 mol HCl(aq) × DH fo HCl(aq)]}
∆Hreact = 2 × (–240.12 kJ mol–1) + 2 × (–167.2 kJ mol–1) + (–393.5 kJ mol–1) + (–285.9 kJ mol–1)
– [(–1131 kJ mol–1) + 2 × (–167.2 kJ mol–1)]
∆Hreact = –28.64 kJ
NaHCO3(s) + HCl(aq) ¾¾ ® Na2+(aq) + Cl–(aq) + H2O + CO2(g)
∆Hreact = ={[1 mol Na+(aq) × DH fo Na+(aq)] + [1 mol Cl–(aq) × DH fo Cl–)]
+ [1 mol CO2 × DH fo CO2] + [1 mol H2O(l) × DH fo H2O(l)]
– {[1 mol NaHCO3 × DH fo NaHCO3] + [1 mol HCl(aq) × DH fo HCl(aq)]}
∆Hreact = (–240.12 kJ mol–1) + (–167.2 kJ mol–1) + (–393.5 kJ mol–1) + (–285.9 kJ mol–1)
– [(–947.7 kJ mol–1) + (–167.2 kJ mol–1)]
∆Hreact = +28.18 kJ
Na2CO3 gives off the greatest amount of heat. The reaction of HCl with NaHCO3 is endothermic.
6.113 We must assume the density of the solution is 1.00 g mL–1 and the specific heat of the solution is
the same as water, 4.184 J g–1 oC–1.
The heat generated by the reaction of the salts with water is given by:
q = 100.0 g × 4.184 J g–1 oC–1 × 5.33 oC = 2230 J
Since the temperature of the water rose when the salts dissolved this value should be negative;
–2230 kJ
Since the reaction involves the formation of a solution from two solids we need to determine the
enthalpy of solution of the two salts. Also, it would be useful to have the enthalpy in units of
kJ g–1.
NH4Cl(s) ¾¾ ® NH4+(aq) + Cl–(aq)
∆Hsoln = [1 mol NH4+ ×( –132.5 kJ mol–1)] + [1 mol Cl– × (–167.2 kJ mol–1)]
– [1 mol NH4Cl × (–315.4 kJ mol–1)] = +15.7 kJ mol–1
1 mol
+15.7 kJ mol–1 × = 0.294 kJ g–1
53.49 g
CaCl2(s) ¾¾ ® Ca2+(aq) + 2Cl–(aq)
∆Hsoln = [1 mol Ca2+ × ( –542.83 kJ mol–1)] + [2 mol Cl– × (–167.2 kJ mol–1)] – [1 mol CaCl2(s) ×
(–795.0 kJ mol–1)] = –82.23 kJ mol–1
1 mol
–82.23 kJ mol–1 × = –0.741 kJ g–1
110.99 g
Now we need to set up an equation for the heat generated when the two solids dissolve. We will
let x be the mass of NH4Cl. Then, the mass of CaCl2 would be 4.56 – x.
x (0.294 kJ g–1) + (4.56 – x)(–0.741 kJ g–1) = –2.230 kJ
x = 1.11 g of NH4Cl 4.56 g – 1.11 g = 3.45 g CaCl2
6.114 From Analyzing and Solving Multi-Concept Problems:
HCl(aq) + NaOH(aq) ¾¾ ® NaCl(aq) + H2O H° = –58 kJ
Net ionic equation:
H+(aq) + OH–(aq) ¾¾ ® H2O H° = –58 kJ (1)
From Practice Exercise 6.14:
6-19
Chapter 6
HC2H3O2 + NaOH(aq) ¾¾ ® NaC2H3O2(aq) + H2O H° = –56 kJ

HC2H3O2 + OH (aq) ¾¾
–
® C2H3O2–(aq) + H2O H° = –56 kJ (2)
The equation for the ionization of acetic acid:
HC2H3O2(aq) H+(aq) + C2H3O2–(aq)
To obtain the thermochemical equation for the ionization of acetic acid reverse Equation (1) and
add it to Equation (2)
H2O ¾¾ ® H+(aq) + OH–(aq) H° = 58 kJ (1)
–
® C2H3O2 (aq) + H2O
–
H° = –56 kJ (2)
–
® C2H3O2 (aq) + H (aq) H° = 2 kJ
– +
Multi-Concept Problems
6.115 The reaction for the combustion of ethanol is:

C2H5OH(l) + 3O2(g) ¾¾ ® 2CO2(g) + 3H2O(l)
∆Hcomb = {[2 mol CO2(g) × Hf°CO2(g)] + [3 mol H2O(l) × Hf°(H2O(l)]}
– [1 mol C2H5(l) Hf°C2H5OH(l)]
= 2 × (–393.5 kJ mol ) + 3 × (–285.8 kJ mol ) – (–277.63 kJ mol–1)
–1 –1
= –1366.77 kJ mol–1 of ethanol

It would be helpful to have this value in kJ per g of ethanol
1 mol
–1366.77 kJ mol–1 C2H5OH × = –29.67 kJ g–1
46.07 g
æ 3.785 L öæ 1000 mL öæ 0.787 g öæ 29.67 kJ ö
1 gal ethanol × ç ÷ç ÷ç ÷ç ÷ = 8.84. × 10 kJ released
4
è gal øè L øè mL øè g ø
6.116 Ca(s) + 2H2O(l) ¾¾ ® Ca(OH)2(s) + H2(g)
∆Hreact = [1 mol Ca(OH)2(s) × Hf°Ca(OH)2] – [2 mol H2O(l) × Hf°H2O(l)]
= –986.59 kJ mol–1 – 2(–285.9 kJ mol–1)
= –415.1 kJ
One mole of Ca(OH)2 is formed in the reaction, so we can calculate the amount of heat released
for Ca(OH)2
1 mol
–415.1 kJ mol–1 Ca(OH)2 × = –5.60 kJ g–1 Ca(OH)2
74.09 g
K(s) + H2O(l) ¾¾
® K+(aq) + OH–(aq) + 1 H2(g)
2
∆Hreact = {[1 mol K+(aq) × Hf°K+(aq)] + [1 mol OH–(aq) × Hf°OH–(aq)]}
– {1 mol H2O(l) × Hf°H2O(l)]
= –252.4 kJ + (–230.0 kJ) – (–285.9 kJ)
= –195.5 kJ for the reaction
One mole of KOH is formed in the reaction, so we can calculate the amount of heat released for
KOH
1 mol
–195.5 kJ mol–1 KOH × = –3.50 kJ g–1 KOH
56.106 g
6-20
Chapter 6
The reaction of Ca with water gives off more heat per mole and per gram.
Now consider the oxidation of the two metals.
Ca ¾¾ ® Ca2+ + 2e– K ¾¾ ® K + + e–
Calcium is a two electron oxidation and potassium is a one electron oxidation.
1 mol Ca(OH) 2
–415.1 kJ mol–1 Ca(OH)2 × = –207.55 kJ mol–1 e–
2 mol e -
1 mol KOH
–195.5 kJ mol–1 × = –195.5 kJ mol–1 e–
1 mol e –
Ca reacting with water gives off more heat per mole of electrons.
6.117 The number of moles of HCl in a 2.5 L bottle can be determined by the following:
12.0 mol HCl L–1 × 2.5 L = 30 mol HCl
The number moles of ammonia in the solution can be determined by the following:
13.4 mol NH3(aq) L–1 x 2.5 L = 33.5 mol NH3(aq)
The neutralization reaction involves one mole each of the acid and base. Note that we have an
excess of NH3, 33.5 mol NH3 versus 30 mol HCl, and thus HCl is the limiting reagent.
50.49 kJ mol–1 HCl × 30 mol HCl = 1515 kJ of heat would be evolved in this reaction.
6.118 The balanced equation is
2AgNO3(aq) + CaCl2(aq) ¾¾ ® 2AgCl(s) + Ca(NO3)2(aq)
Ag (aq) + Cl (aq) ¾¾
+ –
® AgCl(s)
H° = [1 mol AgCl(s) × DH fo AgCl(s)]
– {[1 mol Ag+(aq) × DH fo Ag+(aq)] + [1 mol Cl–(aq) × DH fo Cl–(aq)]}
H° = (–127 kJ) – {(105.58 kJ) + (–167.2 kJ)}
= –65.4 kJ
Moles of ions:
æ 0.225 mol AgNO öæ 1 mol Ag+ ö
mol Ag+ = 0.0950 L AgNO3 çç 3 ÷ç ÷ = 2.14  10–2 mol Ag
÷ ç ÷
è 1 L AgNO3 øè 1 mol AgNO3 ø
æ 0.225 mol CaCl öæ 2 mol Cl – ö
÷ç 1 mol CaCl ÷ = 2.14  10 mol Cl
mol Cl– = 0.0475 L CaCl2 çç 2 ÷ç ÷ –2 –
è 1 L CaCl 2 øè 2ø
–65.4 kJ
qreaction = 2.14  10–2 mol AgCl  = –1.40 kJ
1 mol AgCl
q = mst
qreaction = –qwater
qwater = –(–1.40 kJ) = 1.40 kJ = 1.40  103 J
q
t =
ms
1.40 ´ 103 J
t = = 2.35 °C
142.5 g ´ 4.1485 J g –1 °C –1
tfinal = 23.7 °C + 2.35 °C = 26.1 °C
6-21
Another random document with
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employers in this country of importing European labor under
contract to perform services in the United States at much less than
the market rate of wages, is so great, that, as in the previous case,
human nature cannot resist the temptation, provided the chances of
escaping detection are sufficiently good. And this part of the law, like
that relating to advertising, is of such a nature as to make it
susceptible of continued and extensive evasion by unscrupulous
persons, possessed of such skill and craftiness as characterize the
typical contract labor agent. While there is no way of estimating the
extent of this practice, there is no doubt that only a very small
proportion of the present immigration, from the Mediterranean
countries at least, is innocent of the letter of the law, strictly
interpreted. This is not to say that they are under actual contract to
labor, but that their coming has been encouraged by some sort of
intimation that there would be work awaiting them.
By a recent opinion of the Attorney-General, two essential points
have been laid down in the construction of the contract labor laws, as
follows:
“(1) That they ‘prohibit any offer or promise of employment which
is of such a definite character that an acceptance thereof would
constitute a contract.’
“(2) That the prohibition to encourage the immigration of an alien
by a promise of employment is ‘directed against a promise which
specially designates the particular job or work or employment for
which the alien’s labor is desired.’”[126]
Even under this somewhat liberal interpretation of the laws,
wholesale violations undoubtedly go on. In the words of the
Immigration Commission, “In this way hundreds of immigrants are
annually debarred at United States ports as contract laborers, while
doubtless hundreds of thousands more are admitted who have
practically definite assurances as to the place and nature of their
employment in this country.”
A fuller description of contract labor in general, and of that
particular form of it which is known as the padrone system, will be
given in another connection. The point to be emphasized here is that
it operates as one of the great causes of our present immigration, and
that it continues to exert a powerful, and probably increasing,
influence, in spite of all the efforts of the legislators and officials of
the United States to check it.
The third source of stimulation to emigration is the earlier
immigrant himself. He is probably the greatest factor of all in
induced immigration, and his influence is utilized in various ways by
both emigration agents and labor agents, and made to contribute to
the success of their efforts.
Every stream of immigration must have its origin in some few
individuals, who, the first of their region, break the ties of home and
fatherland, and go to seek their fortune in a new and far-away land.
Upon their success depends the question whether others from the
same district shall follow in their footsteps. If they fail in their
venture, it serves as a discouraging factor as respects further
emigration from that region. But if they succeed, and win a position
which makes them envied in the eyes of their fellow-countrymen, it
furnishes a powerful stimulus to further emigration. Sooner or later,
there will be some who succeed from every region, and the example
of a few successful ones is likely to far outweigh numerous failures.
Something like this is going on in countless remote districts of the
south European countries, and has gone on for decades in every
country which has sent us numbers of immigrants.
Take a typical example. Some Slav peasant, in a little village of
Austria-Hungary, of a more ambitious and adventurous disposition
than most of his fellows, hears of the opportunities in America, and
being dissatisfied with his present lot, decides to try his fortune in
the new world. His first “job” is in a mine in some small town of
Pennsylvania. Accustomed as he is to a low standard of living, he is
able to save a considerable part of the wages which seem munificent
to him. From time to time he writes letters home, telling of his
prosperity. Eventually he saves up enough to purchase a little store
or saloon. Of course there will be a letter telling about that. These
letters are wonderful documents in the eyes of his friends and
relatives at home. Correspondence does not flourish in these regions,
and the receipt of any letter is a matter of great importance. The
arrival of a message from across the sea creates an impression which
it is almost impossible for an American to comprehend. The precious
missive is read aloud in the coffee-houses, and passed from hand to
hand throughout the village. It may even travel to neighboring
hamlets, and make its impression there. The neighbor in America,
and his career, become the foremost topic of conversation for miles
around.
In time all this has its effect. A small group of the original
emigrant’s former neighbors resolve to try their luck too. The most
natural thing, of course, is for them to go to the place where their
friend is. He helps them to find work, tides them over difficulties,
and in various ways makes their life easier and simpler than his had
been. Each of these newcomers also writes letters home, which go
through the same round, and add to the growing knowledge of
America, and the discontent with European life in comparison. Once
started, the movement grows with great rapidity, and the letters from
America increase in geometrical proportion. Other nuclei start up in
other places, recruits are drawn from more distant villages, and the
first little trickling stream becomes a swelling tide.
This is what has come to be known as the chain-letter system.
Multiplied by hundreds of thousands, the foregoing example serves
to illustrate the irresistible network of communications which is
drawing the peasants of Europe to every part of the United States.
This is recognized by all authorities as probably the most powerful
single factor in stirring up emigration from such countries as Italy,
Austria-Hungary, Greece, Bulgaria, etc. Its effect has been
graphically described by a Greek writer in the following words:
“‘Such a one, from such a village, sent home so many dollars
within a year,’ is heard in some village or city, and this news, passed
like lightning from village to village and from city to city, and
magnified from mouth to mouth, causes the farmer to forsake his
plow, the shepherd to sell his sheep, the mechanic to throw away his
tools, the small-grocer to break up his store, the teacher to forsake
his rostrum, and all to hasten to provide passage money, so that they
may embark, if possible, on the first ship for America, and gather up
the dollars in the streets before they are all gone.”[127]
This is a perfectly natural influence, and obviously beyond the
power of any legislation to check, even if that were desirable. When
inspired merely by a friendly interest in the home neighbors, a desire
to keep in touch with them, and a little personal vanity, it is probably
the most harmless of any of the forms of stimulation. When, as all
too frequently happens, the underlying motive is sinister and selfish,
it becomes a source of the greatest deceit and injustice.
When the pioneer emigrant returns to his native village, after some
years of prosperous life in America, his influence and importance are
unbounded. He becomes in truth the “observed of all observers.”
Groups of interested listeners and questioners gather round him
wherever he goes, and hang on his words in breathless awe. His fine,
strange clothes, his sparkling jewelry and gold watch, his easy,
worldly manners, all arouse the greatest admiration. He has to tell
over and over again the story of his career, and describe the wonders
of that far-away land. If such a one is returning to the United States,
it takes no urging on his part to induce a number of his countrymen
to accompany him; they are fairly clinging to the skirts of his
garments, to be taken back. Even if he has come home to remain, his
constant example is there to inspire the youth of the village to follow
in his path. So the “visit home” and the “returned immigrant” add
their weight to the influence of the stream of letters. How universal
this condition has become is evidenced by the fact that in 1909 only
6.3 per cent of all the immigrants admitted to the United States were
not going to join either relatives or friends, according to their
statement; in 1910 the percentage was only 4.9. In 1912 it rose to 7.5.
About six times as many go to join relatives as friends.
Many of the letters from America contain remittances from the
immigrants to their friends and relatives at home. Often these
remittances take the form of prepaid tickets,[128] complete from some
European center or port to the city in America, where the sender is
waiting. Then their influence is absolutely irresistible. The
transportation companies make every effort to make the passage as
simple as possible, and railroad companies in this country make
special immigrant rates, to be used in connection with such tickets. A
large part of the induced immigration of the present day is also
assisted immigration. It is a perfectly natural thing that an
immigrant in this country should wish to be joined by certain of his
relatives on the other side, and, if he is able, should send them the
means to come. This has always been done. In the middle of the
nineteenth century E. E. Hale wrote that a large part of the letters
from Irish to their friends in this country consisted in
acknowledgments of remittances, and requests for more. The
remittances in 1850 are said to have amounted to about four and one
half million dollars. Prepaid tickets were also in use at that date. It is
manifestly impossible to estimate correctly the extent of this
business at the present time. According to the official reports, in
1910, 72.5 per cent of the immigrants had paid for their own tickets,
26.5 per cent had their tickets paid for by a relative, and 1 per cent by
some one other than self or relative. But this showing rests solely
upon the immigrant’s own statement, and is undoubtedly an
underestimate. The suspicion of immigrants whose passage is paid
for them, which characterizes our law, leads many to practice deceit
in this matter. For instance, it is almost impossible to believe that all
but 5.4 per cent of the Greeks had paid their own passage. An
examination of the figures shows that there is a larger proportion of
passages paid by some one besides the immigrant among the old
immigration than among the new. This is explained by the fact that
the old immigration has more of a family character, and that
immigrants are sending for wives and children. This can be
understood only by comparison with the sex and age tables.[129]
Even when these remittances are not in the form of prepaid
tickets, nor are even intended to pay passage in any way, they exert a
powerful influence in stirring up immigration, through the tangible
evidence which they furnish of American possibilities. There could be
no stronger proof of the success of immigrants in the United States
than the constant stream of gold which is flowing from this country
to Europe.
For the sake of clearness, these different forms of stimulation have
been discussed separately. In practice, they overlap and combine in a
variety of complicated relations. The emigration agent is often
himself a returned immigrant; if not, he utilizes all the influences
which arise from the letters, visits, and remittances of actual
immigrants to further his ends. The letters from America are often
misleading or spurious, used by labor agents in this country to entice
others to come. The prepaid ticket is susceptible of a wide variety of
uses. Assistance to emigrants is often furnished, not by well-disposed
friends and relatives, but by loan-sharks, whose motives are wholly
selfish, and whose sole aim is to secure usurious rates of interest for
sums advanced, which are amply protected by mortgages.
As a result of this complex of motives and forces, America has
become a household word even to the remote corners of Europe, and
he who wishes, for any reason, to stir up emigration from any region
finds a fertile field already prepared for him. It is amazing to find
how much an ignorant Greek peasant knows about conditions in
America. The economic situation is, of course, the prime interest. But
there is also a good fund of information about social and political
subjects. There are of course many misconceptions and errors, but it
is evident that the lines of communication between the European
village and the American city are very well established. Similar
conditions prevail in all the immigrant-furnishing countries.
It is impossible to say to just what extent our present immigration
ought to be classified as induced. It is probable that only a very small
part of the total immigration is wholly free from stimulation to some
degree. Certain it is that a very large proportion of it is thoroughly
artificial and induced. The getting of immigrants is now a thoroughly
developed system, planned to serve the needs of every form of
interest which might profit thereby.[130] As to the quality of such
immigration, something has already been said. There is evidently
nothing about the immigrants themselves, or the way in which they
are secured, that serves as a guarantee of their serviceability or value
to this country; as to their own prospects, we can do no better in
closing this chapter than to quote the words of the Commissioner
General; these various operations “often result in placing upon our
shores large numbers of aliens who, if the facts were only known at
the time, are worse than destitute, are burdened with obligations to
which they and all their relatives are parties,—debts secured with
mortgages on such small holdings as they and their relatives possess,
and on which usurious interest must be paid. Pitiable indeed is their
condition, and pitiable it must remain unless good fortune
accompanies the alien while he is struggling to exist and is denying
himself the necessaries of decent living in order to clear himself of
the incubus of accumulated debt. If he secures and retains
employment at fair wages, escapes the wiles of that large class of
aliens living here who prey upon their ignorant compatriots, and
retains his health under often adverse circumstances, all may
terminate well for him and his; if he does not, disaster is the result to
him and them.”[131]
CHAPTER IX
THE EFFECTS OF IMMIGRATION. CONDITIONS OF
EMBARKATION AND TRANSPORTATION
It was remarked in an earlier paragraph that the effects of

immigration were largely a matter of the future. This may have
seemed like too sweeping a statement. Yet it will prove true upon
consideration. In the case of the old immigration there are, to be
sure, certain immediate and superficial effects which may be
postulated with a fair degree of certainty. As an example, we may be
reasonably sure that the old immigration has increased the
proportion of Irish, German, and Scandinavian blood in the
composite American people. But as to the ultimate effects of this
movement upon the social, religious, moral, and economic aspects of
our national life, we can, at best, hazard only a forecast. The reason is
that the effects have not transpired as yet.
“One of the commonest errors of writers on sociological topics is to
allow too little time for the action of social forces. We are inclined to
think that the effects of a certain social phenomenon, which we are
able to detect in our lifetime, are the permanent and final effects. We
forget that these matters may require many generations to work
themselves out. No better illustration of this could be asked for than
that furnished by the case of the negroes in the United States. The
importation of these people began many generations ago. To our
ancestors it undoubtedly seemed a perfectly natural thing to do, and
for centuries it did not occur to anybody to even question its
rightfulness or its expediency. When objections began to be raised,
they were feeble and easily put aside. But at last the presence of this
peculiar class of people in the country involved the nation in a
terrible and bloody conflict, which worked irreparable injury to the
American stock by the annihilation of the flower of southern
manhood, and left us a problem which is probably the greatest one
before the American people to-day—one which we have hardly begun
to solve. There is much of similarity between the case of the negroes
and that of the modern immigrants. To be sure, the newcomers of to-
day are for the most part white-skinned, instead of colored, which
gives a different aspect to the matter. Yet in the mind of the average
American, the modern immigrants are generally regarded as inferior
peoples—races which he looks down on, and with which he does not
wish to associate on terms of social equality. Like the negroes, they
are brought in for economic reasons, to do the hard and menial work
to which an American does not wish to stoop.”[132]
Even in the case of the old immigration, then, the effects are
largely in the future; in the case of the new immigration they are
almost wholly so. We have seen that in regard to racial stock the new
immigration has been predominant for scarcely half a generation.
There are a number of circumstances besides this which make the
immigration problem practically a new one. Certain of the most
important factors which condition it, and many of the aspects which
it presents to the public mind, are new to the men of this generation.
The verification of this statement is to be found in the following
pages; in the present connection it must suffice merely to suggest the
circumstances in which these differences may be looked for. These
may be grouped under six main heads, as follows: (1) the racial stock
of the immigrants; (2) the volume of the immigration current; (3) the
distribution of immigrants in the United States; (4) the economic
conditions of this country; (5) the native birth rate; (6) the quality of
the immigrants.
If the effects of immigration are mainly in the future, the
discussion of them must be, for the most part, theoretical. It is a
discussion of something which is going to happen, or which is likely
to happen, not of something that has happened. This gives it an
element of uncertainty and speculation which is not wholly desirable
in a scientific study. Yet this is the phase of the subject which is by far
the most interesting and important to the average American citizen
who wants to know how this great sociological phenomenon is going
to affect him, and his country, and his relatives and friends. His
attitude toward the question will depend upon what he believes these
effects will be. If it appears to him that immigration will benefit
himself, his country, the immigrants, or humanity in general, he will
favor it; if his belief is to the contrary, his attitude will be one of
opposition. Since there is no certainty as to what the effects will be,
the arguments about immigration are largely composed of attempts
to prove that certain effects have transpired, or to demonstrate that
they will transpire. As a consequence, it comes about that the
discussion of the effects of immigration practically resolves itself into
a consideration of the arguments for and against immigration, and it
will be so treated, for the most part, in the following chapters.
There are three classes of effects of immigration which may be
clearly distinguished, and which will interest different persons in
different degrees. These are the effects upon the United States, the
effects upon the countries of source, and the effects upon the
immigrants themselves. The second and third of these interest the
American citizen only as he is open to broad humanitarian
considerations; the first touches him directly, and may have an
intimate bearing on his personal and selfish interests and pursuits. If
a seemingly disproportionate space is given in this volume to effects
in general, and effects upon the United States in particular, it is
because this is the vital and imperative part of the whole subject to
the people of this nation.
Although the effects of immigration are largely a matter of
speculation and debate, one step may be taken which will help to
make the deductions arrived at as reliable as is possible under the
circumstances. This is a careful investigation of the actual conditions
which surround immigration at the present time, and a comparison
of them with those of the past. Only upon a solid basis of such facts
can any trustworthy predictions be made as to what may be expected
to come about in the future. Accordingly, in preparation for the
discussion of effects, we will attempt to get a clear picture of the
circumstances which surround the immigrant on his journey from
the old world to the new; of his condition when he arrives; of the
character of his life and labor in his new home. In general, the plan
followed will be to take up each set of conditions in turn, and having
ascertained the facts, to try to determine what bearing these seem
likely to have upon the final effects of immigration. This will at times
involve a departure from the strictly logical method of treatment, but
this is unavoidable in such a complicated discussion.
With the sources of our present immigration we are already
familiar. We have seen how they have shifted from the north and
west of Europe to the south and east. It has been stated that the
movement is essentially a European one. This is still emphatically
true. In 1912, 85.8 per cent of all our immigrants came from Europe,
and if we exclude Turkey in Asia (which really is a part of Europe in
the ethnical sense), British North America, Mexico, and the West
Indies, there is very little left of the non-European portion. So it is
still correct, for all important purposes, to regard immigration to the
United States as having its origin in Europe. How long this will
continue, it is of course impossible to say. There are vast reservoirs of
population in Asia, to say nothing of the other continents, which we
have scarcely as yet tapped, and which may reach the point of
emigration with advancing civilization. Whether or not we are to
receive large contingents from these countries in the future will
depend largely upon the attitude of our government. So far, we have
put up the bars before the Chinese, and unless they are lowered,
which hardly seems likely, we need not anticipate any considerable
number of arrivals of this race. Up to 1900 there were only a
comparatively few Japanese in this country. Since then, the rising
tide of immigration from Japan, which threatened to reach large
proportions, has been checked, partly by “a series of measures which
permits the greater part of the administrative problem to rest with
the Japanese government,”[133] which is avowedly opposed to the
emigration of its laboring population, and partly by a presidential
order from the White House on March 14, 1907,[134] denying
admission to Japanese and Korean laborers, who had received
passports to go to Canada, Mexico, or Hawaii, and were using them
to secure admittance to continental United States. While the new
treaty between this country and Japan contains no specific
prohibition of immigration, it is understood that the Japanese
government agrees to prevent the emigration of laborers from that
country to this. A new problem has recently appeared in the Pacific
coast states in the form of an East Indian immigration. The
manifestly undesirable character of this immigration, however, has
led the immigration officials in the Pacific seaports to apply the law
to members of this race with the greatest strictness, so that most, if
not all, of the Hindu laborers applying for admission have been
debarred on the grounds of belief in polygamy, liability to become a
g p yg y y
public charge, or some other provision of the statutes. A similar
attitude on the part of the Canadian immigration officials has been of
assistance in stopping at the outset what might have grown into a
very important current of immigration.[135]
Whatever the future may bring forth, then, our immigration at
present springs from European sources.[136] Every country on the
continent furnishes its contingent, large or small. From the cities,
towns, and villages, most of all from the rural sections, even to the
most remote corners of the back districts, they come, inspired with
great hopes by the emigration agents and the labor contractors, aided
by friends or relatives or future employers on the other side. Homes
and property are mortgaged, the labor of their bodies—even their
very souls—are pledged, to pay their passage. Wives, children, and
sweethearts are left behind. On foot, on donkey back, in rude
carriages and wagons, they travel till the nearest railroad station is
reached. The way is made as easy as possible for them, through the
agency of interested parties, who profit by their coming. The prepaid
ticket avoids much confusion and perplexity. Friends are awaiting
them on the other side. In every large group there are almost certain
to be some who have been over the road before. All the emigrant
needs to do is to allow himself to be passed along submissively from
one stage to another—provided he has the money to pay. For those
who make the way easy must have an ample recompense.
As the seacoast and the port of embarkation draw near, the groups
of emigrants increase in size by constant additions. In the important
emigration ports they arrive by thousands during the busy season.
The provisions for their entertainment, while awaiting the sailing of
the vessel upon which they are to embark, differ in different ports. In
many ports they are required to put up in the cheap hotels and
lodging houses, which, in such cases, abound in the neighborhood of
the harbor. In other ports, the steamship companies maintain
extensive emigrant stations, where emigrants are lodged and cared
for while awaiting transportation. Probably the most elaborate of
these is the emigrant village of the Hamburg-American Line, at
Hamburg. This is located on the left bank of the Elbe, completely
segregated from the city, and is designed to receive only immigrants
from countries where the standard of health is low. It consists of
about twenty-five buildings, and accommodates 5000 persons.
Among the buildings are a large inspection building, a simple hotel,
and a number of living pavilions, each consisting of a dormitory,
living room, baths, etc. There is one large dining hall, with a special
section for Jews, for whom also a separate kitchen is provided. The
religious needs of the emigrants are provided for by a synagogue, a
Catholic church, and a Protestant church.[137]
The provision of the United States law, which requires an
examination and medical inspection at the port of embarkation, is
observed with different degrees of care in different countries and by
different lines. It is to the advantage of the steamship company to
refuse transportation to any individuals who are manifestly
inadmissible to the United States, as their refusal involves their
return at the expense of the company, and in many instances an
additional fine of $100. On the other hand, if there is a fair chance
that the immigrant may succeed in passing the examination, there is
a strong temptation for the steamship company to take him, for the
sake of his passage money. There is a practice, believed to be quite
extensive, among the transportation companies, of compelling an
alien who seems in danger of being debarred, to deposit with the
foreign agent from whom he purchases his ticket a sum sufficient to
cover the cost of his return in case he is refused admission. This is in
direct violation of the United States law, but the difficulty of securing
evidence has prevented the authorities from putting an effective stop
to the practice.[138] Large numbers of would-be emigrants are
nevertheless turned back before embarkation, as a result of the
examination by the steamship company. The proportion of those
detained in this manner to those debarred at the ports of arrival in
the United States is at least four to one.[139] Some companies have
had such a bitter experience in the matter of having their passengers
refused as to lead them to exercise great caution. The Austro-
American Company, which carries a large share of the Greek traffic,
had over 300 emigrants refused at the United States port on one of
their early voyages, and returned to Europe. Since then, they have
adopted the system of having physicians provided for their forty
subagencies in various parts of Greece, who inspect applicants for
tickets, and pass upon them before any document is issued to them
by the agent. If this physician accepts an emigrant, he is given a
medical certificate, makes a deposit toward his ticket, and has space
reserved for him on the steamer. He is then sent on to the port of
embarkation, where the final examination takes place.[140] In this way
large numbers of inadmissible immigrants are kept from leaving
their native village, and are spared the expense and disappointment
of the trip to the port of embarkation.
The examination at the port of embarkation is differently
conducted at different seaports. As a rule the medical examination is
made by a physician employed by the steamship company, either the
ship’s doctor, or a specially engaged physician. But at some ports the
American consul chooses the physician, though the steamship
company pays him. At Naples, Palermo, and Messina, by a special
arrangement between the two governments, the examination is made
by officers of the United States Public Health and Marine Hospital
Service, who examine steerage passengers and recommend the
rejection of those who are likely to be refused admission to the
United States. Their action is unofficial, but their suggestions are
always complied with. Under the quarantine law of the United States
the American consular officers are also required to satisfy themselves
of the sanitary condition of passengers and ships sailing for United
States ports. In addition to the medical examination, a long list of
questions is put to the immigrant, in accordance with the
requirements of the United States law. His answers are recorded on
the manifest, which is later put into the hands of the inspecting
officer at the port of arrival, who repeats the same questions and
notes whether the answers tally. Vaccination and the disinfection of
the passenger’s baggage are important parts of the preparation of
emigrants for the journey to America. The differing degree of care
exercised in this examination at the different ports is indicated by the
fact that the proportion of immigrants refused at the port of arrival
for medical causes, to the total number embarked from the different
ports, varies from 1 to 163 at the Piræus and 1 to 165 at Bremen, to 1
to 565 at Antwerp and 1 to 597 at Fiume.
A large amount of transatlantic traffic passes through Germany
from neighboring states, and to protect herself against having large
numbers of foreign emigrants refused at her ports, and left in a
destitute and helpless condition in her territory, Germany has
compelled the steamship companies to establish control-stations on
the German-Russian and German-Austrian borders. There are
fourteen of these stations, thirteen on the frontier, and one near
Berlin. All emigrants from eastern Europe who are intending to pass
through German territory to ports of embarkation are examined at
these stations, and those who do not comply with the German law, or
who are evidently inadmissible to the United States, are turned back.
This is a wise and humane provision, for the condition of the
emigrant, who, having spent his all to pay his passage to America,
and traveled a long distance to the seaboard, finds himself refused at
the port of embarkation, is often pitiable in the extreme.[141]
The governments of most European countries do not regard a large
emigration with favor, partly because of the withdrawal of men from
military service, partly because of the economic loss resulting from
the departure of so large a part of the laboring class. Most of them
exercise some control over emigration, and, in particular, endeavor
to combat the activities of the emigration agents, which, however,
they are as powerless to check as is the United States. Nevertheless,
there is practically no effort to prohibit emigration altogether, as it is
recognized as a natural and irresistible movement. Italy exercises the
greatest care for the welfare of her immigrants of any European
nation.
Practically all of the immigrants who are crossing for the first time,
and probably a majority of those who have made the trip before,
travel in the steerage. The second cabin is patronized by the more
prosperous of the immigrants who have been in the United States
previously, and by others who know themselves to be inadmissible,
and hope in this way to avoid a searching inspection. The great bulk
of the emigrants, however, having passed their preliminary
examination, flock up the steerage gangway into the ship which is to
convey them to America. At the top of the ladder stands a ship’s
officer who examines their tickets and their certificates of
vaccination (sometimes a little purple mark stamped on the wrist),
and in certain cases searches them for concealed weapons. They are
then allowed to proceed to the interior of the ship, and find their way
to such berths as suit their fancy, and are not already occupied,
within the limits of the section of the ship assigned to them.
Steerages are usually divided into three compartments, more or less
completely separated from each other; one is for men without wives,
another for women traveling alone, and the third for families.
Steerages on the transatlantic vessels are divided into two main
classes, designated by the Immigration Commission as the old-type
or old steerage, and the new-type or new steerage. The former class
predominates on the Mediterranean lines; the latter is found on
some of the better ships of the north Atlantic service. Some ships are
equipped with both kinds. The old-type steerage is still the typical
one, and is found on the majority of vessels bringing immigrants to
the United States. It is in such a steerage that the average immigrant
gets his first introduction to America—for everything after he leaves
the port of embarkation is closely identified with America in his
mind. It is in this type of steerage that the student of immigration is
primarily interested.
Steerages of this type all bear a general resemblance to each other,
and once seen can never be forgotten. Imagine a large room, perhaps
seven feet in height, extending the entire breadth of the ship, and
about one third of its length. The floor and ceiling are sometimes of
iron, but more often of wood. Through the center of the room, very
probably, descends the shaft to the hold. This room is filled with a
framework of iron pipes, with only sufficient space left to serve as
aisles or passageways. This framework is so constructed as to form a
series of berths or bunks, adjoining each other laterally, and in two
tiers vertically. The dimensions of these berths are usually about six
feet by two, with approximately two and one half feet between
berths, and about the same space between the lower berth and the
deck below, and the upper berth and the deck above. In each berth a
network of strap iron serves for the support of a coarse mattress,
upon which a pillow and a cheap blanket are the only bedding. Often
a life-preserver takes the place of the pillow. Thus the room is filled
with a double layer of beds, with only space enough between for the
passengers to reach them. On some of the older ships wooden bunks
may still be found. Such a room will sometimes accommodate as
many as three hundred passengers, and is duplicated in other parts
of the ship, and on the successive decks upon which immigrants are
carried.
In their provisions for steerage passengers most transportation
lines aim to trim as close to the minimum requirements of the law as
possible. The immigrant-carrying business is a purely money-making
enterprise, and humanitarian considerations have no place in it. The
good effects which might result from free competition are practically
eliminated by the recent agreement dividing territory, which has
been mentioned above.[142] There is no other force to compel
transportation companies to go one whit beyond the legal
requirements in an effort to make their steerage passengers
comfortable.
The open deck space reserved for steerage passengers is usually
very limited, and situated in the worst part of the ship, subject to the
most violent motion, to the dirt from the stacks and the odors from
the hold and galleys. The only provisions for eating are frequently
shelves or benches along the sides or in the passageways of sleeping
compartments. Some ships have separate rooms, used for dining and
recreation purposes, but these are usually wholly inadequate to
accommodate all the steerage passengers. Frequently, too, they are
planned without the least regard to cleanliness, as when the dining
table, upon which the dishes remain set, is placed directly below an
open grating, through which the filth and dirt may fall from the shoes
of passers-by. Toilet rooms are wholly inadequate in number, are
poorly designed, and often wholly uncared for during most of the
voyage. The resulting conditions are almost unbelievable. Toilets are
sometimes placed directly alongside the only passages leading to the
steerage quarters, so that one must pass them, and breathe their
horrible stench, every time he passes in or out. The law requires
separate wash rooms for men and women, but this is a distinction
which is frequently ignored, men and women using the same rooms
promiscuously. The provisions for washing are wholly inadequate.
There are only a few taps, and usually the only water provided is cold
salt water, which must be used for all purposes, including the
washing of dishes. The law requires that hospitals for steerage
passengers be provided, but as they are not open to seasick
passengers, they fail of their greatest usefulness.
The arrangements for feeding steerage passengers differ on
different vessels, but there are two main systems. In the first, each
passenger is furnished a cheap set of eating utensils at the beginning
of the voyage, which remain in his possession till the close, and
sometimes permanently. At meal time the passengers form in line,
and pass before stewards who have large kettles of food, and serve
out the rations to each. Passengers may eat at tables if there are any
and they can find places; otherwise, wherever they can. After the
meal, they must wash their own dishes, and stow them away for
future use. Under the second system, the women and children
receive slightly better attention, being given first place at such tables
as there are. The most essential utensils are placed by stewards, and
washed by them afterwards. The food is served in large pans, one for
each table, which are passed along a line of stewards from the galley,
in the manner of a bucket brigade. This is all the table service there
is. The men receive even less attention. They are divided into groups
of six, and each group is given two large tin pans, and tin plates, tin
cups, and cutlery enough for all. Each man takes his turn at going
after the food, and in caring for the dishes. The men eat wherever
they can find a place.
Life under such circumstances must of necessity be disgusting and
degrading, whatever the character or desires of the individual. The
only part of the whole ship which the steerage passenger has a right
to call in any sense his own is the few square feet contained in his
berth. Here he must keep all of his personal belongings. His hand
baggage must be stored in it, or hung from the pipes above his head.
If there are eating utensils committed to his keeping, they must be
concealed in some corner of the bunk when not in use. This is the
only place to which he may retire in the search of even the semblance
of privacy. It is the only place where he can recline during the
daytime, except upon the open deck. The berths receive absolutely no
attention from the stewards from the beginning of the voyage to the
end. Is it any wonder that they become untidy, mussed, and ill
smelling? The blankets provided are usually wholly inadequate for
cold weather, so that passengers are absolutely compelled to sleep in
their day clothing for warmth.
The ventilation of the steerage is almost always inadequate,
growing worse the farther down one goes. The congestion is intense,
and even if every provision were made for cleanliness, the air would
inevitably become foul. Unfortunately such provision is not made.
There are no sick-cans provided for the use of steerage passengers,
and the vomitings of the seasick are allowed to lie unattended to for
hours. Sometimes a steward comes around with a can of sawdust or
sand, but that is of little avail. Add to this the odors of bodies not too
clean, the reek of food, and the awful stench of the toilet rooms, and
the atmosphere of the steerage becomes such that it is a marvel that
human flesh can endure it. It is a fact that many of the passengers lie
in their berths for the greater part of the voyage, in a stupor caused
by breathing the vitiated air, indifferent to everything around them,
unless it be to their meals. If one attempts to better things by going
on deck, and remains above for any length of time, he finds it almost
impossible to go below again. There are practically only two
alternatives; either to go below for only a few hours of sleep, and
spend practically all the time on deck, or to spend all the time below.
Even if the immigrants desired to keep personally clean, there is
practically no opportunity, owing to the inadequacy of the wash
rooms, the absence of towels, soap, etc., and the absolute lack of
privacy. Only one who was trained to make the very most of such
facilities could maintain his decency under such conditions; the bulk
of the immigrants lack even the elements of such training.
The food served to steerage passengers is, according to almost all
investigators, usually sufficient in quantity, and originally of good
quality. But in the majority of cases it is so poorly cooked and served
in such an unappetizing way as to render it most unsatisfactory. An
average menu reads very well; it is only when one actually
undertakes to eat the food, as served to the immigrants, that the real
quality appears. There is usually a canteen, or bar, where drinks,
candy, fruit, etc., may be secured by those who can pay for them, and
stewards sometimes turn an extra penny by securing food from the
second cabin for steerage passengers who make the arrangement
with them.
One of the worst conditions prevailing in the steerage, upon which
the investigators of the Immigration Commission lay great stress, is
the indecent and immoral attitude and conduct of the men, including
the crew as well as the passengers, toward the women. The stories
which are told of the constant persecution of immigrant women,—
unprovided as they are with any means of privacy,—even by those
whose duty it is to protect them, are almost unbelievable, but are well
substantiated. As one investigator wrote, only a set of instantaneous
photographs could give an adequate idea of the demoralizing
attentions to which women and girls are subjected, until even the
most self-respecting of them sometimes weaken under the strain.
The United States law, of course, aims to prevent these abuses, but it
is powerless, without better machinery for enforcement than is
provided.
All of these conditions are naturally aggravated by crowding, and
are usually more pronounced on the westward than on the eastward
trip, since the steerage is ordinarily more congested coming to the
United States. It is a marvel that even the ignorant, uncultured,
stolid peasants of Europe can find life tolerable under such
conditions. Yet they do, and manage to get some enjoyment out of it
besides. There are songs and games and dances to while away the
time. Especially when the ship stops at any intermediate port the
deck throngs with immigrants, men, women, and children, seeking
recreation in their own way.
On the whole, the old-type steerage is the poorest possible
introduction to, and preparation for, American life. It inevitably
lowers the standards of decency, even of the immigrants, and often
breaks down their moral and physical stamina. It shatters their
bright visions of American life, and lands them cynical and
embittered. One of the first steps in the improvement of the
immigration situation should be the abolition of the old-type
steerage.
The new-type steerage, which is found on some lines carrying
immigrants from north Europe, was the result of competition for the
traffic, which led certain companies to improve their facilities. The
traffic agreement above referred to, by eliminating this competition,
has prevented the extension of this type of steerage to other lines,
and other ships. In general, the new-type steerage is a modified
second cabin, with simpler and plainer accommodations, and less
attendance. Separate staterooms are provided, having from two to
eight berths in each; in some cases the berths are of the old steerage
type. The blankets are adequate, and towels, mirrors, etc., are
provided. On some lines the stewards are responsible for the care of
the berths and staterooms. There are regular dining rooms, properly
cared for; the food is abundant, and when carefully prepared, of good
quality. Facilities for washing and toilet are superior to the old
steerage, and greater segregation of the sexes is secured. The air is
still bad, but not so absolutely intolerable, and most of the flagrant
abuses of the old-type steerage are avoided. Old and new steerages
are sometimes found on the same vessel, in which case the latter is
known as third class. The difference in price between the two does
not at all correspond to the wide difference in accommodations; in
general, the price of steerage passage is much nearer to that of
second cabin than the relative service would seem to warrant. This
tends to disprove the claim sometimes made that the steamship
companies cannot afford to furnish better accommodations to
steerage passengers without materially raising the price, as does the
fact that passengers are actually being carried in the new-type
steerage, with a profit, at a moderate charge.
Throughout their long journey from their native villages to the
portals of America, the immigrants are very much at the mercy of
those into whose hands they have committed themselves for
transportation. Their treatment differs with different companies, but
all too often they are handled like so many cattle, or even worse, like
so many articles of inanimate freight.[143]
The Immigration Commission recommends that a law be passed
requiring United States government officials, both men and women,
to be placed on all ships carrying third class or steerage passengers,
at the expense of the companies, and that inspectors in the guise of
immigrants should occasionally be sent across in the steerage. This
ought certainly to bring about a decided improvement in conditions,
for at present there is no provision, on the part of this government,
for enforcing the steerage laws, or looking after the welfare of
passengers on the voyage. Ships are subject to inspection after they
arrive in port, but conditions are very different then from what they
are in mid-ocean. As the ship approaches shore, toilet rooms and
wash rooms are cleaned up, disinfectants are used, and everything is
made to appear more proper and orderly. That such supervision and
inspection is capable of producing beneficial results is proved by the
fact that on ships carrying an Italian royal commissioner, conditions
are very much superior to those on others.

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6.3 T = Tfinal – Tinitial = 32 °C – 25 °C = 7 °C

6.5 The amount of heat transferred into the water is:

6.14 Net ionic equation: HC2H3O2 + OH– ¾¾® H2O + C2H3O2–

6.15 Multiply the reaction and the H° by 3:

Cu 2O(s) + 1/2 O 2(g)

6.25 H° = [sum DH fo products] – [sum DH fo reactants]

6.27 H° = [sum DH fo products] – [sum DH fo reactants]

– {[1 mol NaOH × DH fo NaOH(s)] + [1 mole HCl × DH fo HCl(g)]}

6.27 (a) Kinetic energy must increase.

6.46 (a) The standard enthalpy of reaction, DH fo , changes sign.

æ 1 mol CCl 4 öæ 153.81 g CCl öæ 1 kg CCl ö

6.53 t = 15.0 C – 25.0 C = –10.0 C

6.55 qFe = (85.0 g Fe)(0.4498 J g–1 C–1)(35.0 C – 85.0 C) = –1912 J

mCu = 165 g of copper

J æ 0.586 cal öæ 4.184 J öæ 46.08 g C H OH ö

6.63 HNO3(aq) + KOH(aq) ¾¾ ® KNO3(aq) + H2O(l)

6.64 HCHO2(aq) + NaOH(aq) ¾¾ ® NaCHO2(aq) + H2O(l)

6.65 (a) C3H8(g) + 5O2(g) ¾¾ ® 3CO2(g) + 4H2O(l)

The enthalpy change for the reaction NO(g) + 1

6.86 The equation we want is Cu(s) + 1

6.92 (a) Mg(s) + Cl2(g) + 2H2(g) + O2(g) ¾¾

6.93 (a) DH o = {[1 mol O2(g)  DH fo O2(g)] + [2 mol H2O(l)  DH fo H2O(l)]}

6.94 (a) DH fo = {[1 mol HCl(g)  DH fo HCl(g)] + [1 mol CH3Cl(g)  DH fo CH3Cl(g)]}

= 12(–393.5 kJ) + 11(–285.9 kJ) – (–5.65 × 103 kJ) = –2.22 × 103 kJ

6.99 qgranite = (2000 g)(0.803 J g–1 °C–1)(tfinal – 95 C)

– {[4 mol C2H5NO2(s) × DH fo C2H5NO2(s)] + [9 mol O2(g) × DH fo O2(g)]}

6.103 The equation may be written as: 1

2HCl(aq) + 2KOH(aq) ¾¾ ® 2KCl(aq) + 2H2O(l) H° = –115 kJ

= {[12 mol CO2(g) × HfCO2(g) + [11 mol H2O(l) × HfH2O(l)]}

6.107 Simply add the two together to get:

(b) Water: q < 0 Copper: q > 0

+ [1 mol CO2 × DH fo CO2] + [1 mol H2O(l) × DH fo H2O(l)]}

HC2H3O2 + NaOH(aq) ¾¾ ® NaC2H3O2(aq) + H2O H° = –56 kJ

6.115 The reaction for the combustion of ethanol is:

= –1366.77 kJ mol–1 of ethanol

It was remarked in an earlier paragraph that the effects of

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