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Chemical Thermodynamics
1
Chapter Goals
Heat Changes and Thermochemistry
The First Law of Thermodynamics
Some Thermodynamic Terms
Enthalpy Changes
Calorimetry
Themochemical Equations
Standard States and Standard Enthalpy Changes
Standard Molar Enthalpies of Formation, ∆Hfo
2
Chapter Goals
Hess’s Law
Bond Energies
Relationship of ∆H and ∆E
Entropy, S
5
The First Law of Thermodynamics
Exothermic
reactions generate
specific amounts
of heat.
This is because the
potential energies
of the products are
lower than the
potential energies
of the reactants.
6
The First Law of Thermodynamics
There are two basic ideas of importance for
thermodynamic systems.
❏ Chemical systems tend toward a state of minimum
potential energy.
Some examples of this include:
H2O flows downhill.
Objects fall when dropped.
The energy change for these two examples is:
Epotential = mgh
∆Epotential = mg(∆h) 7
The First Law of Thermodynamics
Chemical systems tend toward a state of
maximum disorder.
Common examples of this are:
A mirror shatters when dropped and does not
reform.
It is easy to scramble an egg and difficult to
unscramble it.
Food dye when dropped into water disperses.
8
The First Law of Thermodynamics
This law can be stated as, “The combined
amount of energy in the universe is constant.”
The first law is also known as the Law of
Conservation of Energy.
Energy is neither created nor destroyed in
chemical reactions and physical changes.
9
Some Thermodynamic Terms
The substances involved in the chemical and
physical changes under investigation are called the
system.
In chemistry lab, the system is the chemicals inside the
beaker.
The environment around the system is called the
surroundings.
The surroundings are outside the beaker.
The system plus the surroundings is called the
universe.
10
Some Thermodynamic Terms
The set of conditions that specify all of the
properties of the system is called the
thermodynamic state of a system.
For example the thermodynamic state could include:
The number of moles and identity of each substance.
The physical states of each substance.
The temperature of the system.
The pressure of the system.
11
Some Thermodynamic Terms
The properties of a system that depend only on the state of
the system are called state functions.
State functions are always written using capital letters.
The value of a state function is independent of pathway.
An analog to a state function is the energy required to climb a
mountain taking two different paths.
E1 = energy at the bottom of the mountain
E1 = mgh1
E2 = energy at the top of the mountain
E2 = mgh2
∆E = E2-E1 = mgh2 – mgh1 = mg(∆h)
12
Some Thermodynamic Terms
Notice that the energy change in moving from the
top to the bottom is independent of pathway but
the work required may not be!
Some examples of state functions are:
T, P, V, ∆E, ∆H, and S
Examples of non-state functions are:
n, q, w
13
Some Thermodynamic Terms
In thermodynamics we are often interested in
changes in functions.
We will define the change of any function X as:
∆X = Xfinal – Xinitial
If X increases ∆X > 0
If X decreases ∆X < 0.
14
Enthalpy Change
Chemistry is commonly done in open beakers
on a desk top at atmospheric pressure.
Because atmospheric pressure only changes by
small increments, this is almost at constant
pressure.
The enthalpy change, ∆H, is the change in
heat content at constant pressure.
∆H = qp
15
Enthalpy Change
∆Hrxn is the heat of reaction.
This quantity will tell us if the reaction produces
or consumes heat.
If ∆Hrxn < 0 the reaction is exothermic.
If ∆Hrxn > 0 the reaction is endothermic.
∆Hrxn = Hproducts - Hreactants
∆Hrxn = Hsubstances produced - Hsubstances consumed
Notice that this is ∆Hrxn = Hfinal – Hinitial
16
Calorimetry
A coffee-cup
calorimeter is used to
measure the amount of
heat produced (or
absorbed) in a reaction
at constant P
This is one method to
measure qP for
reactions in solution.
17
Calorimetry
If an exothermic reaction is performed in a
calorimeter, the heat evolved by the reaction is
determined from the temperature rise of the solution.
This requires a two part calculation.
Amount of heat Amount of heat Amount of heat
= +
released by reaction absorbed by calorimeter absorbed by solution
Amount of heat gained by calorimeter is called the heat
capacity of the calorimeter or calorimeter constant.
The value of the calorimeter constant is determined by adding a
specific amount of heat to calorimeter and measuring the temperature
rise.
18
Calorimetry
Example 15-1: When 3.425 kJ of heat is
added to a calorimeter containing 50.00 g of
water the temperature rises from 24.00oC to
36.54oC. Calculate the heat capacity of the
calorimeter in J/oC. The specific heat of water
is 4.184 J/g oC.
This is a four part calculation.
19
Calorimetry
1. Find the temperature change.
(
= ( 50.00 g) 4184
. J 0
g C ) ( 12.54 C)
0
= 262337
. J ≈ 2623 J 20
Calorimetry
1. Find the heat absorbed by the calorimeter.
Take the total amount of heat added to calorimeter and
subtract the heat absorbed by the water.
3.425 kJ = 3425 J
( 3425 J - 2623 J ) = 802 J
1. Find the heat capacity of the calorimeter.
(heat absorbed by the calorimeter)/(temperature change)
802 J
0
= 63955
. J 0 ≈ 64.00 J 0
C C
12.54 C 21
Calorimetry
Example 15-2: A coffee-cup calorimeter is
used to determine the heat of reaction for the
acid-base neutralization
CH3COOH(aq) + NaOH(aq) → NaCH3COO(aq) + H2O()
When we add 25.00 mL of 0.500 M NaOH at
23.000oC to 25.00 mL of 0.600 M CH3COOH
already in the calorimeter at the same
temperature, the resulting temperature is
observed to be 25.947oC. 22
Calorimetry
The heat capacity of the calorimeter has
previously been determined to be 27.8 J/0C.
Assume that the specific heat of the mixture is the
same as that of water, 4.18 J/g0C and that the
density of the mixture is 1.02 g/mL.
23
Calorimetry
This is a three part calculation.
1. Calculate the amount of heat given off in the reaction.
temperature
temperature
temperature change
change
change
∆T = (
∆T = ( 25.947 - 23.000
25.947 - 23.00000 ) 0 C = 2.947
23.000) C
0
2.947 CC C
C == 2.947 00
(
q = ( 51.0 g) 418
. J
) ( 2.947 C) = 628 J
g0 C
0
25
Calorimetry
Determine ∆H for the reaction under the conditions of the
experiment.
We must determine the number of moles of reactants consumed
which requires a limiting reactant calculation.
CH
CH33COOH
COOH ( aq ) ++NaOHNaOH ( aq ) → → NaCH 3COO ( aq( )aq+) H 2 O2( l ) ( l )
NaCH 3COO +H O
( aq ) ( aq )
0.500 mmol NaOH
( 25.00 mL NaOH) 0 .500 mmol NaOH × ×
( 25 .00 mL NaOH )
1 mL NaOH
1 mL NaOH
1 mmol NaCH 3COO =12.5 mmol NaCH COO
1 mmol
1 NaCH
mmol COO
NaOH 3
3
= 12.5 mmol NaCH 3COO
1 mmol NaOH 0.600 mmol CH 3COOH
( 25.00 mL CH 3COOH ) ×
1 mL CH 3COOH
1 mmol NaCH 3COO
=15.0 mmol NaCH 3COO 26
1 mmol CH 3COOH
Calorimetry
Finally, calculate the ∆Hrxn based on the limiting reactant
calculation.
12.5 mmol = 0.0125 mol
709.9 J
∆ H rxn = = 56792 J / mol ≈ 56.8 kJ / mol
0.0125 mol
27
Thermochemical Equations
Thermochemical equations are a balanced chemical
reaction plus the ∆H value for the reaction.
For example, this is a thermochemical equation.
C5 H12( ) + 8 O 2(g) → 5 CO 2(g) + 6 H 2 O ( ) + 3523 kJ
1 mole 8 moles 5 moles 6 moles
The stoichiometric coefficients in thermochemical
equations must be interpreted as numbers of moles.
1 mol of C5H12 reacts with 8 mol of O2 to produce 5
mol of CO2, 6 mol of H2O, and releasing 3523 kJ is
referred to as one mole of reactions. 28
Thermochemical Equations
This is an equivalent method of writing thermochemical
equations.
C5 H12( ) + 8 O 2(g) → 5 CO 2(g) + 6 H 2 O ( ) ∆H orxn = - 3523 kJ
∆H < 0 designates an exothermic reaction.
∆H > 0 designates an endothermic reaction
29
Thermochemical Equations
Example 15-3: Write the thermochemical
equation for the reaction in Example 15-2.
You do it!
CH 3COOH ( aq ) + NaOH ( aq ) → NaCH 3COO( aq ) + H 2O( l ) ∆H = -56.8 kJ / mol
30
Standard States and Standard
Enthalpy Changes
Thermochemical standard state conditions
The thermochemical standard T = 298.15 K.
The thermochemical standard P = 1.0000 atm.
Be careful not to confuse these values with STP.
Thermochemical standard states of matter
For pure substances in their liquid or solid phase the standard
state is the pure liquid or solid.
For gases the standard state is the gas at 1.00 atm of pressure.
For gaseous mixtures the partial pressure must be 1.00 atm.
For aqueous solutions the standard state is 1.00 M
concentration. 31
Standard Molar Enthalpies of
Formation, ∆Hf o
3
2 H 2( g ) + 2 O 2( g ) + 1
4 P4( s ) → H 3 PO 4( s ) + 1281 kJ
o
∆ H f H 3PO 4 ( s ) = − 1281 kJ / mol
34
Standard Molar Enthalpies of
Formation, ∆Hf o
36
Standard Molar Enthalpies of
Formation, ∆Hf o
4 Al ( s) + 3 O 2( g ) → 2 Al 2 O 3( s)
o
from Appendix K, ∆ H f Al 2O 3 = − 1676 kJ / mol
1 mol Al 2 mol Al 2 O 3
? kJ = 15.0 g Al × × ×
27.0 g Al 4 mol Al
− 1676 kJ
= − 466 kJ
1 mol Al 2 O 3
37
Hess’s Law
Hess’s Law of Heat Summation states that the enthalpy
change for a reaction is the same whether it occurs by
one step or by any (hypothetical) series of steps.
Hess’s Law is true because ∆H is a state function.
If we know the following ∆Ho’s
[1] 4 FeO(s) + O 2(g) → 2 Fe 2O3(s) ∆H o = −560 kJ
[ 2] 2 Fe(s) + O 2(g) → 2 FeO(g) ∆H o = −544 kJ
[ 3] 4 Fe(s) + 3 O 2(g) → 2 Fe 2O3(s) ∆H o = −1648 kJ
38
Hess’s Law
For example, we can calculate the ∆Ho for reaction [1] by properly adding
(or subtracting) the ∆Ho’s for reactions [2] and [3].
Notice that reaction [1] has FeO and O2 as reactants and Fe2O3 as a
product.
Arrange reactions [2] and [3] so that they also have FeO and O2 as reactants
and Fe2O3 as a product.
Each reaction can be doubled, tripled, or multiplied by half, etc.
The ∆Ho values are also doubled, tripled, etc.
If a reaction is reversed the sign of the ∆Ho is changed.
∆H 0
2 x [−2] 2(2 FeO ( s ) →2 Fe ( s ) + O 2( g ) ) 2( +544 ) kJ
[ 3] 4 Fe( s ) +3 O 2( g ) →2 Fe 2 O 3( s ) −1648 kJ
[ 1] 4 FeO ( s ) + O 2( g ) →2 Fe 2 O 3 −560 kJ
39
Hess’s Law
Example 15-7: Given the following equations
and ∆Ho values ∆H o ( kJ )
[1] 2 N 2( g ) + O 2( g ) → 2 N 2 O ( g ) 164.1
[2] N 2( g ) + O 2( g ) → 2 NO ( g ) 180.5
[3] N 2( g ) + 2 O 2( g ) → 2 NO 2 ( g ) 66.4
2 [
3 × 2
] 3 N
2 2( gg) + 33 O O → 3 NO 270.75
22 22((gg)) → 3 NO ( (gg) ) 270.75
2 [
1 × − 3 NO
] 2( g ) → 1 N
2 2( g ) + O 2 ( g ) - 33.2
N 2 O ( g ) + NO 2( g ) → 3 NO ( g ) 155.5
41
Hess’s Law
The + sign of the ∆Ho value tells us that the reaction is
endothermic.
The reverse reaction is exothermic, i.e.,
o
3 NO ( g ) → N 2 O ( g ) + NO 2 ( g ) ∆H = -155.5 kJ
42
Hess’s Law
Hess’s Law in a more useful form.
For any chemical reaction at standard conditions, the
standard enthalpy change is the sum of the standard molar
enthalpies of formation of the products (each multiplied
by its coefficient in the balanced chemical equation)
minus the corresponding sum for the reactants.
∆H 0
rxn = ∑ n ∆H 0
f products − ∑ n ∆H 0
f reactants
n n
n = stoichiometric coefficients
43
Hess’s Law
Example 15-8: Calculate the ∆H o298 for the
following reaction from data in Appendix K.
C3 H 8(g) + 5 O 2(g) → 3 CO 2(g) + 4 H 2 O ( )
44
Hess’s Law
Example 15-8: Calculate ∆Ho298 for the following
reaction from data in Appendix K.
C3 H 8( g ) + 5 O 2( g) → 3 CO 2( g) + 4 H 22O(( ll))
o
∆ H 298
298 = [ o
3∆ H ff CO
CO22( gg)
o
+ 4∆ H f HH2OO( ll)
2
] −[ oo
∆ H ff CC3 HH8( g )
3 8( g )
++ 55∆∆H oo
HffOO22( (gg) ) ]
= { [ 3( − 3935
. ) + 4( − 2858 .. )) ++ 55((00))] } kJ
. )] − [ ( − 1038
1038 kJ
= -2211.9 kJ
∆ H o298 = − 22119
. kJ, and so the reaction is exothermic.
45
Hess’s Law
Application of Hess’s Law and more algebra allows us to
calculate the ∆Hfo for a substance participating in a reaction
for which we know ∆Hrxno , if we also know ∆Hfo for all other
substances in the reaction.
Example 15-9: Given the following information, calculate ∆
Hfo for H2S(g).
2 H 2S( g ) + 3 O 2( g ) → 2 SO 2( g ) + 2 H 2 O ( l ) ∆ H o298 = -1124 kJ
∆ H of ? 0 - 296.8 - 285.8
(kJ / mol)
You do it!
46
Hess’s Law
[ ] [
∆H o298 = 2∆H of SO 2 ( g ) + 2∆H of H 2O ( l ) − 2∆H of H 2S( g ) + 3∆H of O 2 ( g ) ]
− 1124 kJ = { [ 2( −296.8 ) + 2( −285.8] − [ 2∆H o
f H 2S( g ) ]}
+ 3( 0 ) kJ
∆H of H 2S( g ) = −20.6 kJ
47
Bond Energies
Bond energy is the amount of energy required to
break the bond and separate the atoms in the gas
phase.
To break a bond always requires an absorption of energy!
A - B( g ) + bond energy → A ( g ) + B( g )
H - Cl ( g ) + 432 kJ mol → H ( g ) + Cl ( g )
48
Bond Energies
Table of average bond energies
Molecule Bond Energy (kJ/mol)
F2 159
Cl2 243
Br2 192
O2 (double bond) 498
N2 (triple bond) 946
49
Bond Energies
Bond energies can be calculated from other ∆Ho298 values.
50
Bond Energies
Bond energies can be calculated from other ∆Ho298
values
Example 15-9: Calculate the bond energy for hydrogen
fluoride, HF.
H - F(( gg)) +
+ BE HF →
BEHF
HF →H
→ H(((ggg))) ++
H +FF( (g(gg) )) atoms
atomsNOT
NOTions
ions
or or
or
H - F(( gg)) →
→HH(( gg)) ++ FF((gg) ) ∆∆HHo298
298 ==BE
o
BEHFHF
HF
∆H oo
∆H 298 = ∆H [
oo
298 = ∆Hff H
+ ∆H oo
H( (gg) ) + ∆Hf f FF
( g( )g )]] [ [
− ∆H oo
− ∆Hf HF
f HF ]]
( g() g )
52
Bond Energies
NH 3( g ) → N ( g ) + 3 H ( g ) ∆H o
298 = 3 BE N -H
∆H o
298 [
= ∆H o
f N( g ) + 3 ∆H o
f H( g ) ] − [∆H o
f NH 3( g ) ]
∆H o
298 = { [ (472.7) + 3(218)] − [ − 46.11]} kJ
∆H o
298 = 1173 kJ
1173 kJ
average BE N -H = = 391 kJ mol N -H bonds
3
53
Bond Energies
In gas phase reactions ∆Ho values may be
related to bond energies of all species in the
reaction.
o
∆H 298 = ∑ BE reactants − ∑ BE products
54
Bond Energies
Example 15-11: Use the bond energies listed
in Tables 15-2 and 15-3 to estimate the heat
of reaction at 25oC for the reaction below.
CH 4(g) + 2 O 2(g) → CO 2(g) + 2 H 2 O (g)
∆H o298 = [4 BE C-H + 2 BE O =O ] - [2 BE C =O + 4 BE O-H ]
55
Bond Energies
CH 4(g) + 2 O 2(g) → CO 2(g) + 2 H 2 O (g)
∆H o
298 = [4 BE C-H + 2 BE O = O ] - [2 BE C= O + 4 BE O-H ]
∆H o298 = {[4 (414) + 2 (498)] - [2 (741) + 4 (464)]} kJ
∆H o298 = - 686 kJ
56
Changes in Internal Energy, ∆E
The internal energy, E, is all of the energy
contained within a substance.
This function includes all forms of energy such as
kinetic, potential, gravitational, electromagnetic,
etc.
The First Law of Thermodynamics states that the
change in internal energy, ∆E, is determined by
the heat flow, q, and the work, w.
57
Changes in Internal Energy, ∆E
∆
∆EE
∆ E==E=products
EE − E
products
products reactants − E reactants
− E reactants
∆
∆
∆EE =
E==q + w
q +qw + w
q > 0 if heat is absorbed by the system.
q > 0 if heat is absorbed by the system.
q < 0 if heat is absorbed by the system.
q ><00ififtheheat
w is absorbed
surroundings do workby on the system.
the system.
w < 0 if the system does work on the surroundings.
58
Changes in Internal Energy, ∆E
∆E is negative when energy is released by a system
undergoing a chemical or physical change.
Energy can be written as a product of the process.
59
Changes in Internal Energy, ∆E
∆E is positive when energy is absorbed by a system
undergoing a chemical or physical change.
Energy can be written as a reactant of the process.
60
Changes in Internal Energy, ∆E
Example 15-12: If 1200 joules of heat are added to a
system in energy state E1, and the system does 800
joules of work on the surroundings, what is the :
o energy change for the system, ∆Esys?
∆E = E 2 - E1 = q + w
∆E = 1200 J + (-800 J)
∆E = 400 J
∆E sys = + 400 J 61
Changes in Internal Energy, ∆E
o energy change of the surroundings, ∆Esurr?
You do it!
∆E surr = −400 J
62
Changes in Internal Energy, ∆E
o energy of the system in the new state, E2?
∆E sys = E 2 - E1
E 2 = E1 + ∆E sys
= E1 + 400 J
63
Changes in Internal Energy, ∆E
In most chemical and physical changes, the
only kind of work is pressure-volume work.
Pressure is force per unit area.
force F
P = = 2
area d
64
Changes in Internal Energy, ∆E
Volume is distance cubed.
3
V = d
P∆V is a work term, i.e., the same units are used for
energy and work.
F 3
( )
P∆ V = 2 d = F × d ← which is work
d
65
Changes in Internal Energy, ∆E
This movie shows a gas doing work to prove
that P∆V is a different way of writing work.
66
Changes in Internal Energy, ∆E
Using the ideal gas law PV = nRT, we can look at
volume changes of ideal gases at constant T and P
due to changes in the number of moles of gas
present, ∆ngas.
PV = nRT
(
P( ∆V ) = ∆n gas RT )
∆ngas = (number of moles of gaseous products) - (number of
moles of gaseous reactants)
67
Changes in Internal Energy, ∆E
Work is defined as a force acting through a specified
distance.
w = F × d = -P∆V = -( ∆n gas ) RT
Thus we can see that w = -( ∆n gas ) RT
at constant T and P.
Consequently, there are three possibilities for volume
changes:
68
Changes in Internal Energy, ∆E
When Then Examples
❏ V2 = V1 P∆V = 0 CO (g) + H 2 O (g) → H 2 (g) + CO 2(g)
∆ngas = 0 2 mol gas 2 mol gas
75
Relationship of ∆H and ∆E
Example 15-13: In Section 15-5, we noted
that ∆Ho = -3523 kJ/mol for the combustion
of n-pentane, n-C5H12. Combustion of one
mol of n-pentane at constant pressure releases
3523 kJ of heat. What are the values of the
work term and ∆E for this reaction?
C5 H12( ) + 8 O 2(g) → 5 CO 2(g) + 6 H 2 O ( )
76
Relationship of ∆H and ∆E
Determine the work done by this reaction.
You do it!
C5 H12( ) + 8 O 2(g) → 5 CO 2(g) + 6 H 2 O ( )
8 mol gas 5 mol gas
81
Entropy, S
Entropy is a measure of the disorder or
randomness of a system.
As with ∆H, entropies have been measured and
tabulated in Appendix K as So298.
When:
∆S > 0 disorder increases (which favors
spontaneity).
∆S < 0 disorder decreases (does not favor
spontaneity).
82
Entropy, S
From the Second Law of Thermodynamics, for a
spontaneous process to occur:
84
Entropy, S
Entropy changes for reactions can be determined
similarly to ∆H for reactions.
∆S o
298 = ∑ nS o
products − ∑ nS o
reactants
n n
85
Entropy, S
Example 15-14: Calculate the entropy change
for the following reaction at 25oC. Use
appendix K.
→
2 NO 2(g) ← N 2 O 4(g)
You do it!
86
Entropy, S
→N O
2 NO 2(g) ← 2 4(g)
3 NO ( g ) →
← N 2 O ( g ) + NO 2( g )
You do it!
88
Entropy, S
3 NO ( g ) →
← N 2 O ( g ) + NO 2( g )
∆S 0
298 =S 0
N 2O( g ) +S 0
NO 2 ( g ) −3S 0
NO ( g )
∆G 0
298 = ∑ n∆G 0
products − ∑ n∆G 0
reactants
n n
92
Free Energy Change, ∆G,
and Spontaneity
Example 15-16: Calculate ∆Go298 for the
reaction in Example 15-8. Use appendix K.
C3 H 8( ) + 5 O 2(g) → 3 CO 2(g) + 4 H 2 O ( )
You do it!
93
Free Energy Change, ∆G,
and Spontaneity
C3 H 8(g) + 5 O 2(g) → 3 CO 2(g) + 4 H 2 O ( )
∆G orxn = [3∆G of CO 2(g) + 4∆G of H 2O ( ) ] − [∆G of C3H8(g) + 5∆G of O 2(g) ]
= {[3(−394.4) + 4(−237.3) − [(−23.49) + 5(0)]} kJ mol
= −2108.5 kJ mol
∆Go298 < 0, so the reaction is spontaneous at
standard state conditions.
If the reaction is reversed:
∆Go298 > 0, and the reaction is nonspontaneous at
standard state conditions. 94
The Temperature
Dependence of Spontaneity
Free energy has the relationship ∆G = ∆H -T∆S.
Because 0 ≤ ∆H ≥ 0 and 0 ≤ ∆S ≥ 0, there are four
possibilities for ∆G.
∆H ∆S ∆G Forward reaction spontaneity
<0 >0 <0 Spontaneous at all T’s.
<0 <0 T dependent Spontaneous at low T’s.
>0 >0 T dependent Spontaneous at high T’s.
>0 <0 >0 Nonspontaneous at all T’s.
95
The Temperature
Dependence of Spontaneity
96
The Temperature
Dependence of Spontaneity
Example 15-17: Calculate ∆So298 for the following reaction.
In example 15-8, we found that ∆Ho298= -2219.9 kJ, and in
Example 15-16 we found that ∆Go298= -2108.5 kJ.
C o 12([−
H +
2219
8 O − (→
.92(g) − 2108
5 CO ]
.5)2(g)
kJ+ 6 H 2 O ( )
∆S =
5 )
298 K o
∆G = ∆
o
H − T ∆S o
∆H o − ∆G o
= ∆S o
T
97
The Temperature
Dependence of Spontaneity
∆So298 = -374 J/K which indicates that the
disorder of the system decreases .
For the reverse reaction,
3 CO2(g) + 4 H2O(g) → C3H8(g) + 5 O2(g)
∆So298 = +374 J/K which indicates that the
disorder of the system increases .
98
The Temperature
Dependence of Spontaneity
Example 15-18: Use thermodynamic data to estimate
the normal boiling point of water.
→
H 2 O ( ) ← H 2 O (g)
Because this is an equlibrium process ∆G = 0.
∆H
Thus ∆H = T∆S and T =
∆S
99
The Temperature
Dependence of Spontaneity
o
assume ∆H@ BP ≈ ∆H 298
o o o
∆H = ∆H H 2O(g) − ∆H H 2O( l )
∆H = [ −2418
o
. )] J K
. − ( −2858
o o
∆H = +44.0 kJ@25 C 100
The Temperature
Dependence of Spontaneity
assume ∆S @ BP ≈ ∆S 0
rxn
∆S 0
rxn =S 0
H 2O( g ) −S 0
H 2O ( )
∆S 0
rxn = [188.7 − 69.91] J K
∆S 0
rxn = 118.8 J
K or 0.1188 kJ
K
101
The Temperature
Dependence of Spontaneity
o
∆H ∆H 44.0 kJ
T = ≈ o = = 370 K
∆ S ∆ S 0.1188 kJ K
o
370 K - 273 K = 97 C
102
The Temperature
Dependence of Spontaneity
Example 15-19: What is the percent error in
Example 15-18?
% error =
( 370 - 373) K
× 100% = −0.80% error
373 K
% error of less than 1%!!
103
Synthesis Question
When it rains an inch of rain, that means that
if we built a one inch high wall around a piece
of ground that the rain would completely fill
this enclosed space to the top of the wall.
Rain is water that has been evaporated from a
lake, ocean, or river and then precipitated
back onto the land. How much heat must the
sun provide to evaporate enough water to rain
1.0 inch onto 1.0 acre of land?
104
1 acre = 43,460 ft 2
Synthesis Question
1 in = 2.54 cm 1 ft = 30.5 cm
(1 ft ) 2
= ( 30.5 cm ) = 930 cm
2 2
930 cm
( )
2
1 acre = 43,460 ft 2
2
1 ft
= 4.04 ×10 cm
7 2
(
volume = 4.04 ×10 cm 7 2
)( 2.54 cm)
= 1.03 ×10 cm
8 3 105
Synthesis Question
1g
mass of water = 1.03 × 10 cm 3 8 3
cm
= 1.03 × 108 g of water
1 mol
(
moles of water = 1.03 × 10 g 8
)
18 g
= 5.71×106 mol
∆H vaporization of water = 44.0 kJ
mol
(
heat sun must supply = 5.71×106 mol 44.0 kJ )( mol
)
= 2.51× 10 kJ 8 106
Group Question
When Ernest Rutherford, introduced in Chapter 5,
gave his first lecture to the Royal Society one of the
attendees was Lord Kelvin. Rutherford announced
at the meeting that he had determined that the earth
was at least 1 billion years old, 1000 times older than
Kelvin had previously determined for the earth’s
age. Then Rutherford looked at Kelvin and told him
that his method of determining the earth’s age based
upon how long it would take the earth to cool from
molten rock to its present cool, solid form
107
Group Question
was essentially correct. But there was a new, previously
unknown source of heat that Kelvin had not included in his
calculation and therein lay his error. Kelvin apparently
grinned at Rutherford for the remainder of his lecture.
What was this “new” source of heat that Rutherford knew
about that had thrown Kelvin’s calculation so far off?
108
End of Chapter 15
Fireworks are beautiful exothermic
chemical reactions.
109