CHEMICAL THERMODYNAMICS

Chapter 6

1
2
Chapter Goals
Heat Changes and Thermochemistry
1. The First Law of Thermodynamics
2. Some Thermodynamic Terms
3. Enthalpy Changes
4. Calorimetry
5. Themochemical Equations
6. Standard States and Standard Enthalpy Changes
7. Standard Molar Enthalpies of Formation, DHfo

3
Chapter Goals
8. Hesss Law
9. Bond Energies
10. Changes in Internal Energy, DE
11. Relationship of DH and DE
12. Spontaneity of Physical and Chemical Changes
13. The Two Aspects of Spontaneity
14. The Second Law of Thermodynamics
15. Entropy, S
16. Free Energy Change, DG, and Spontaneity
17. The Temperature Dependence of Spontaneity

4
The First Law of Thermodynamics
Thermodynamics is the study of the changes in
energy and transfers of energy that accompany
chemical and physical processes.
In this chapter we will address 3 fundamental
questions:

Will two (or more) substances react when they are mixed
under specified conditions?
If they do react, what energy changes and transfers are
associated with their reaction?
If a reaction occurs, to what extent does it occur?

5
The First Law of Thermodynamics
Exothermic reactions release energy in the form of heat.
For example, the combustion of propane is exothermic.

C 3 H 8 (g) 5 O 2(g) 3 CO 2(g) 4H 2 O ( ) 2.22 10 3 kJ

The combustion of n-butane is also exothermic.

2 C 4 H 10(g) 13 O 2(g) 8 CO 2(g) 10 H 2 O ( ) 5.78 10 3 kJ

6
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.

7
The First Law of Thermodynamics
There are two basic ideas of importance for
thermodynamic systems.
1. 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
DEpotential = mg(Dh)

8
The First Law of Thermodynamics
2. 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.

9
The First Law of Thermodynamics
First 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.

10
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.

11
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.

12
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
DE = E2-E1 = mgh2 mgh1 = mg(Dh)

13
 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, DE, DH, and S
Examples of non-state functions are = path function:
n, q (heat), w, d (distance)

14
 Some Thermodynamic Terms
In thermodynamics we are often interested in changes in
functions.
We will define the change of any function X as:
DX = Xfinal Xinitial
If X increases DX > 0
If X decreases DX < 0.

15
Some Thermodynamic
Terms
m m

q Open system

q
Close system

Isolated system

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Open system= material, energy can escape
Close system=energy
Isolated system= none

17
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, DH, is the change in heat
content at constant pressure.
DH = qp

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Enthalpy Change
DHrxn is the enthalpy of reaction.
This quantity will tell us if the reaction produces or
consumes heat.
If DHrxn < 0 the reaction is exothermic.
If DHrxn > 0 the reaction is endothermic.
DHrxn = Hproducts - Hreactants
DHrxn = Hsubstances produced - Hsubstances consumed
Notice that this is DHrxn = Hfinal Hinitial

19
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.

20
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 calorimete r 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.

21
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.

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Calorimetry
1. Find the temperature change.

DT = 36.54 - 24.00 C = 12.54 C 0 0

2. Find the heat absorbed by the water in going from

24.000C to 36.540C.
q P mCDT

= 50.00 g 4184
. J
0
g C 12.54 C
0

262337
. J 2623 J
23
3. 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
4. Find the heat capacity of the calorimeter.
(heat absorbed by the calorimeter)/(temperature change)

802 J
0
63.955 J
0
C
64.00 J
0
C
12.54 C

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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.

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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.

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Calorimetry
This is a three part calculation.
1. Step 1 Calculate the amount of heat given off in the reaction.

temperature
temperature
temperature change
change
change
DT =
DT = 25.947 - 23.000
25.947 - 00 0 C = 2.947
23.000 C
23.000 00 0
2.947 CC C
C == 2.947
heatabsorbed
heat absorbed
byby calorimeter
calorimeter
q =
q = 2.947
2.9470 C 27.8
0
J
0

C 27.8 C 819
819
J
. J
0. JC

mass of solution in calorimeter

102
. g
25.00 mL + 25.00 mL 510
. g
mL

27
 heat absorbed by solution
q = mCDT

q = 51.0 g 418
. J
g0 C 2.947 C 628 J
0

total amount of heat produced by reaction

q = 81.9 J + 628 J = 709.9 J

28
Calorimetry
2. Step 2 Determine DH 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.
aqaq NaCH
CH 3COOH CH 3COOH aq + NaOH NaCH 3COO aq +H O l H 2 O
aq + NaOH 3COO aq2 + l
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 NaCH
1 mmol COO
NaOH 3
3
12.5 mmol NaCH 3COO
1 mmol NaOH 0.600 mmol CH 3COOH
25.00 mL CH COOH
3
1 mL CH 3COOH
1 mmol NaCH 3COO
15.0 mmol NaCH 3COO
1 mmol CH 3COOH 29
Calorimetry
3. Step 3 Finally, calculate the DHrxn based on the
limiting reactant calculation.
12.5 mmol = 0.0125 mol
709.9 J
DH rxn 56792 J / mol 56.8 kJ / mol
0.0125 mol

30
 Thermochemical Equations
Thermochemical equations are a balanced chemical
reaction plus the DH value for the reaction.
For example, this is a thermochemical equation.

C 5 H 12( ) 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.
31
Thermochemical Equations
This is an equivalent method of writing thermochemical
equations.
C5H12( ) 8 O2(g) 5 CO2(g) 6 H 2O( ) DHorxn - 3523 kJ
DH < 0 designates an exothermic reaction.
DH > 0 designates an endothermic reaction

32
Thermochemical Equations
Example 15-3: Write the thermochemical equation for
the reaction in Example 15-2.
You do it!

33
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.

34
Standard Molar Enthalpies of
Formation, DHfo

The standard molar enthalpy of formation is defined as

the enthalpy for the reaction in which one mole of a
substance is formed from its constituent elements.
The symbol for standard molar enthalpy of formation is DHfo.
The standard molar enthalpy of formation for MgCl2 is:

Mg s Cl 2 g MgCl 2 s 6418
. kJ
DH f MgCl 2 s
o
6418
. kJ / mol

35
 Standard Molar Enthalpies of
Formation, DHfo

Standard molar enthalpies of formation have been

determined for many substances and are tabulated in
Table 15-1 and Appendix K in the text.
Standard molar enthalpies of elements in their most
stable forms at 298.15 K and 1.000 atm are zero.
Example 15-4: The standard molar enthalpy of formation for
phosphoric acid is -1281 kJ/mol. Write the equation for the
reaction for whichDHorxn = -1281 kJ.
P in standard state is P4
Phosphoric acid in standard state is H3PO4(s)
You do it!

36
 Standard Molar Enthalpies of
Formation, DHfo

3
2 H2g 2 O2g 14 P4s H3PO4s 1281 kJ
DHf H3PO4 s
o
1281 kJ / mol

37
Standard Molar Enthalpies of
Formation, DHfo
Example 15-5: Calculate the enthalpy change for
the reaction of one mole of H2(g) with one mole of
F2(g) to form two moles of HF(g) at 25oC and one
atmosphere.
H 2 g F2 g 2 H F g
std. state std. state std. state
for this rxn. D H o298 2 D H of
from A ppendix K , D H of 271 kJ / m ol
D H o298 2 m ol 271 kJ / m ol 542 kJ

38
Standard Molar Enthalpies of
Formation, DHfo

Example 15-6: Calculate the enthalpy change for the

reaction in which 15.0 g of aluminum reacts with
oxygen to form Al2O3 at 25oC and one atmosphere.
You do it!

39
 Standard Molar Enthalpies of
Formation, DHfo
4 Al s + 3 O 2g 2 Al 2 O 3s
from Appendix K, DH f Al2O3
o
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
40
Hesss Law
Hesss 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.
Hesss Law is true because DH is a state function.
If we know the following DHos

1 4 FeO(s) O 2(g) 2 Fe2O 3(s) DH o 560 kJ

2 2 Fe(s) O 2(g) 2 FeO(g) DH o 544 kJ
3 4 Fe(s) 3 O 2(g) 2 Fe2O 3(s) DH 1648 kJ
o

41
 Hesss Law
For example, we can calculate the DHo for reaction [1] by properly
adding (or subtracting) the DHos 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 DHo values are also doubled, tripled, etc.
If a reaction is reversed the sign of the DHo is changed.
DH 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 3s 1648 kJ

1 4 FeO s O 2 g 2 Fe 2 O 3 560 kJ
42
Hesss Law
Example 15-7: Given the following equations and
DHovalues DH 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
calculate DHo for the reaction below.

N 2 O g + NO 2 g 3 NO g DH o ?
You do it!
43
Hesss Law
Use a little algebra and Hesss Law to get the
appropriate DHovalues
DHDoH(kJ)
o
D o
(kJ) (kJ)
H
1112NN22OOg1g
11
22 ON22ggg
N2N + 1N1 O + 1 O-82.05
2 2 gO
+ 2g2g 2 2 g-82.05
- 82.05
3 2 3 3 N
2 2 2 2g 2 22g 2g 232NO g
2 3 N3 + 3 O 3 NO g 270.75
+ O g 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

44
 Hesss Law
The + sign of the DHovalue tells us that the reaction is
endothermic.
The reverse reaction is exothermic, i.e.,

3 NO g N 2 O g + NO 2 g DH o
= - 155.5 kJ

45
Hesss Law
Hesss 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.

DH 0
rxn n DH 0
f products n DH 0
f reactants
n n

n stoichiome tric coefficien ts

46
Hesss Law

47
Hesss Law
Example 15-8: Calculate the DH o298 for the
following reaction from data in Appendix K.
C3H8(g) 5 O2(g) 3 CO2(g) 4 H 2O( )

48
Hesss Law
Application of Hesss Law and more algebra allows us to
calculate the DHfofor a substance participating in a
reaction for which we know DHrxno , if we also know
DHfofor all other substances in the reaction.
Example 15-9: Given the following information, calculate
DHfo for H2S(g).
2 H2Sg + 3 O2g 2 SO2g +2 H2Ol DHo298 = -1124 kJ
DHof ? 0 -296.8 -285.8
(kJ / mol)
You do
it!
49
Hesss Law
DH 2DH
o
298
o
2DH
f SO2 g
o
2DH
f H2O l
o
f H2S g 3DHof O2 g
1124 kJ 2(2968 . 2DH
. ) 2(2858 o
f H2S g
3(0) kJ

now we solve for DHof H2S g

2DHof H2S g 412

. kJ

DHof H2S g 206

. kJ

50
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

51
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

52
Bond Energies
Bond energies can be calculated from otherDHo298values.

53
Bond Energies
Bond energies can be calculated from
otherDHo298values
Example 15-9: Calculate the bond energy for hydrogen
fluoride, HF.
HH H BE
gFgg
- F-- F H
BEHFHF Hggg FFgg atoms
atomsNOT
atoms NOT
NOT ions
ions
ions
or or
H gFgg
- F-- F
HH H F
H ggg Fggg
DDDHH oo BE
298 BE
Ho298
298
BE
HF
HFHF

D oo
DH 298
H DH oo

298 DH ff H DH oo

DH oo
H gg DHff FFgg DHf fHF
gg
HF

DH o298 218.0 kJ + 78.99 kJ 271 kJ

DH o298 568.0 kJ BE for HF 54
 Bond Energies
Example 15-10: Calculate the average N-H bond energy in
ammonia, NH3.
You do it!

55
Bond Energies
In gas phase reactions DHo values may be related to
bond energies of all species in the reaction.

DH 298
o
BE reactants BE products

56
 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)

DH o298 [4 BE C- H 2 BE O O ] - [2 BE C O 4 BE O -H ]

57
Bond Energies
CH 4(g) 2 O 2(g) CO 2(g) 2 H 2 O (g)
DH o
298 [4 BE C-H 2 BE O O ] - [2 BE C O 4 BE O -H ]
DH o298 [4 (414) 2 ( 498)] - [2 (741) 4 (464)] kJ
DH o298 - 686 kJ

58
Changes in Internal Energy, DE
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, DE, is determined by the heat flow, q,
and the work, w.

59
Changes in Internal Energy, DE
DE E products E reactants
DE q w
q 0 if heat is absorbed by the system.
q 0 if heat is released by the system.
w 0 if the surroundin gs do work on the system.
w 0 if the system does work on the surroundin gs.

60
Changes in Internal Energy, DE
DE 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.

C 5 H12 ( ) 8 O 2(g) 5 CO 2(g) 6 H 2 O ( ) 3.516 10 3 kJ

DE - 3.516 10 3 kJ

61
Changes in Internal Energy, DE
DE 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.

5 CO 2(g) 6 H 2 O ( ) 3.516 10 3 kJ C 5 H12 ( ) 8 O 2(g)

DE 3.516 10 3 kJ

62
Changes in Internal Energy, DE
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 :
1. energy change for the system, DEsys

63
Changes in Internal Energy, DE
2. energy change of the surroundings, DEsurr
You do it!

64
Changes in Internal Energy, DE
3. energy of the system in the new state, E2

65
 Changes in Internal Energy, DE
In most chemical and
physical changes, the
only kind of work is
pressure-volume work or
expansion work, PV work
Pressure is force per unit
area.

force F
P = 2
area d
66
Changes in Internal Energy, DE
Volume is distance cubed.
3
V = d
PDV is a work term, i.e., the same units are used for
energy and work.

F 3

PDV = 2 d F d which is work
d
=w
67
 Changes in Internal Energy, DE
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,
Dngas.

PV = nR T

P D V D n g as R T

Dngas = (number of moles of gaseous products) - (number of

moles of gaseous reactants)
68
Changes in Internal Energy, DE
Work is defined as a force acting through a specified
distance.

w F d -PDV -Dn gas RT

Thus we can see that w -Dn gas RT
at constant T and P.
Consequently, there are three possibilities for volume
changes:

69
Changes in Internal Energy, DE
When Then Examples
1. V2 = V1 PDV = 0 CO (g) H 2 O (g) H 2 (g) CO 2(g)
Dngas = 0
2 mol gas 2 mol gas

2. V2 > V1 PDV > 0 Zn (s) 2 HCl (aq) ZnCl 2(aq) H 2(g)

Dngas > 0 0 mol gas 1 mol gas

3. V2 < V1 PDV < 0 N 2(g) 3 H 2(g) 2 NH 3(g)

Dngas < 0 4 mol gas 2 mol gas

70
 Changes in Internal Energy, DE
Consider the following gas phase reaction at constant
pressure at 200oC.

2 NO g + O 2 g 2 NO 2 g

3 mol gas 2 mol gas

V2 V1 thus DV 0 and PDV 0.

Consequent ly, w - PDV 0.
Work is done on system by surroundin gs.
71
 Changes in Internal Energy, DE
Consider the following gas phase reaction at constant
pressure at 1000oC.

PCl5 g PCl3g Cl 2 g

1 mol gas 2 mol gas
V2 V1 thus DV 0 and PDV 0.
Consequent ly, w - PDV 0.
Work is done by the system on the surroundin gs.
72
Relationship of DH and DE
The total amount of heat energy that a system can
provide to its surroundings at constant temperature
and pressure is given by
DH= DE + P DV
which is the relationship between DH and DE.
DH = change in enthalpy of system
DE = change in internal energy of system
PDV = work done by system

73
Relationship of DH and DE

We know that
DH = qP.
Here we define DH = DE + PDV.
Are these two definitions compatible?
Remember DE = q + w.
We have also defined w = -PDV .
Thus DE = q + w = q -PDV
Consequently, DH = q- PDV + PDV = q
At constant pressure DH = qP.

74
 Relationship of DH and DE
For reactions in which the volume change is very small
or equal to zero.

For small volume changes,

DV 0 and PDV 0.
Since DH DE PDV then
DH DE.
For no volume change,
DH DE. 75
Relationship of DH and DE
Change in enthalpy, DH, or heat of reaction is amount of
heat absorbed or released when a reaction occurs at
constant pressure.
The change in energy, DE, is the amount of heat absorbed
or released when a reaction occurs at constant volume.
How much do the DH and DE for a reaction differ?
The difference depends on the amount of work performed by the
system or the surroundings.

76
Relationship of DH and DE
A bomb calorimeter
device to measure heat
evolved/absorbed by
reaction occur at
constant volume

77
 Relationship of DH and DE
Example 15-13: In Section 15-5, we noted that DHo = -
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 DE for this reaction?

C5H12( ) 8 O2(g) 5 CO2(g) 6 H 2O( )

78
 Relationship of DH and DE
Determine the work done by this reaction.
You do it!

C 5 H12( ) 8 O 2(g) 5 CO 2(g) 6 H 2 O ( )

8 mol gas 5 mol gas

Since DH o - 3523 kJ/mol, we know that T 298 K.

w - PDV - (Dn gas )RT
Dn gas 5 8 mol - 3 mol
w -(-3 mol)(8.314 J
mol K )( 298 K) 7433 J 7.433 kJ
79
Relationship of DH and DE
Now calculate the DE for this reaction from the
values of DH and w that we have determined.
You do it!

80
Spontaneity of Physical and
Chemical Changes
Spontaneous changes happen without any
continuing outside influences.
A spontaneous change has a natural direction.
For example the rusting of iron occurs
spontaneously.
Have you ever seen rust turn into iron metal without
man made interference?
The melting of ice at room temperature occurs
spontaneously.
Will water spontaneously freeze at room temperature?

81
The Two Aspects of Spontaneity
An exothermic reaction does not ensure spontaneity.
For example, the freezing of water is exothermic but
spontaneous only below 0oC.
An increase in disorder of the system also does not
ensure spontaneity.
It is a proper combination of exothermicity and
disorder that determines spontaneity.

82
The Second Law of Thermodynamics
The second law of thermodynamics states, In
spontaneous changes the universe tends towards
a state of greater disorder.
Spontaneous processes have two requirements:
1. The free energy change of the system must be
negative.
2. The entropy of universe must increase.
Fundamentally, the system must be capable of doing useful work
on surroundings for a spontaneous process to occur.

83
Entropy, S
Entropy is a measure of the disorder or randomness of a
system.
As with DH, entropies have been measured and
tabulated in Appendix K as So298.
When:
DS > 0 disorder increases (which favors spontaneity).
DS < 0 disorder decreases (does not favor spontaneity).

84
Entropy, S
From the Second Law of Thermodynamics, for a
spontaneous process to occur:

D S universe D S system D S surroundings 0

In general for a substance in its three states of
matter:

Sgas > Sliquid > Ssolid

85
Entropy, S
The Third Law of Thermodynamics states, The
entropy of a pure, perfect, crystalline solid at 0 K is
zero.
This law permits us to measure the absolute values
of the entropy for substances.
To get the actual value of S, cool a substance to 0 K, or as
close as possible, then measure the entropy increase as
the substance heats from 0 to higher temperatures.
Notice that Appendix K has values of S not DS.

86
Entropy, S
Entropy changes for reactions can be determined
similarly to DH for reactions.

DS o
298 nS o
products nS o
reactants
n n

87
 Entropy, S
Example 15-14: Calculate the entropy change for the
following reaction at 25oC. Use appendix K.

2 NO2(g) N 2O 4(g)
You do it!

88
Entropy, S
N O
2 NO 2(g) 2 4(g)

DSorxn n Soproducts n Soreactants

n n

SoN 2 O 4 (g ) 2SoNO2 (g )
(304.2 J mol K ) 2( 240.0 J mol K )
175.8 J mol K or - 0.1758 kJ mol K
The negative sign of DS indicates that the system is
more ordered.
If the reaction is reversed the sign of DS changes.
For the reverse reactionDSo298= +0.1758 kJ/K
The + sign indicates the system is more disordered.
89
 Entropy, S
Example 15-15: Calculate DSo298 for the reaction below.
Use appendix K.

3 NOg N 2 O g NO 2 g
You do it!

90
Entropy, S
3 NOg
N 2 O g NO2 g
DS 0
298 S 0
N 2O g S 0
NO 2 g 3S 0
NO g

219.7 240.0 - 3210.4 J mol K

172.4 J mol K or - 0.1724 kJ
mol K

Changes in DS are usually quite small compared to

DE and DH.
Notice that DS has units of only a fraction of a kJ while
DE and DH values are much larger numbers of kJ.
91
 Free Energy Change, DG,
and Spontaneity
In the mid 1800s J. Willard Gibbs determined the
relationship of enthalpy, H, and entropy, S, that
best describes the maximum useful energy
obtainable in the form of work from a process at
constant temperature and pressure.
The relationship also describes the spontaneity of a
system.
The relationship is a new state function, DG, the
Gibbs Free Energy.
DG = DH - TDS (at constant T & P)
92
Free Energy Change, DG,
and Spontaneity
The change in the Gibbs Free Energy, DG, is a
reliable indicator of spontaneity of a physical
process or chemical reaction.
DG does not tell us how quickly the process occurs.
Chemical kinetics, the subject of Chapter 16, indicates the rate of
a reaction.
Sign conventions for DG.
DG > 0 reaction is nonspontaneous
DG = 0 system is at equilibrium
DG < 0 reaction is spontaneous

93
 Free Energy Change, DG,
and Spontaneity
Changes in free energy obey the same type of
relationship we have described for enthalpy, DH, and
entropy, DS, changes.

DG 0
298 nD G 0
products nD G 0
reactants
n n

94
 Free Energy Change, DG,
and Spontaneity
Example 15-16: Calculate DGo298 for the reaction in
Example 15-8. Use appendix K.

C3H8( ) 5 O 2(g) 3 CO 2(g) 4 H 2O( )

You do it!

95
Free Energy Change, DG,
and Spontaneity
C 3 H 8(g) 5 O 2(g) 3 CO 2(g) 4 H 2 O ( )
DG orxn [3DG of CO 2 (g ) 4DG of H 2O ( ) ] [ DG of C3H 8(g ) 5DG of O 2 (g ) ]
{[ 3( 394.4) 4( 237.3) [( 23.49) 5(0)]} kJ mol
2108.5 kJ mol
DGo298 < 0, so the reaction is spontaneous at standard state
conditions.
If the reaction is reversed:
DGo298 > 0, and the reaction is nonspontaneous at standard
state conditions.

96
The Temperature
Dependence of Spontaneity
Free energy has the relationship DG = DH -TDS.
Because 0 DH 0 and 0 DS 0, there are four
possibilities for DG.
DH DS DG Forward reaction
spontaneity
<0 >0 <0 Spontaneous at all Ts.
<0 <0 T dependent Spontaneous at low Ts.
>0 >0 T dependent Spontaneous at high Ts.
>0 <0 >0 Nonspontaneous at all
Ts.
97
 The Temperature
Dependence of Spontaneity
Free energy has the relationship DG = DH -TDS.
Because 0 DH 0 and 0 DS 0, there are
four possibilities for DG.
DH DS DG Forward
reaction spontaneity
<0 >0 <0 Spontaneous at all Ts.
<0 <0 T dependent Spontaneous at low Ts.
>0 >0 T dependent Spontaneous at high Ts.
>0 <0 >0 Nonspontaneous at all Ts.

98
 The Temperature
Dependence of Spontaneity
Example 15-17: Calculate DSo298 for the following reaction.
In example 15-8, we found that DHo298= -2219.9 kJ, and in
Example 15-16 we found that DGo298= -2108.5 kJ.

DS o

.95H12(
2219C 2108
)
.5O
8 kJ 5 CO 2(g) 6 H 2 O ( )
2(g)
298 K
D G o
D H o
T D S o

DSo 0.374 kJ -374 J o

K DHK DG o TDSo
DH o DG o
DS o
T

99
The Temperature
Dependence of Spontaneity
DSo298 = -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)
DSo298 = +374 J/K which indicates that the disorder of
the system increases .

100
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 DG 0.
DH
Thus DH TDS and T
DS

101
The Temperature
Dependence of Spontaneity

assume DH@ BP DH 298

o

DH
o
DH H 2O(g)
o
DH H 2O( l )
o

DH 2418
o
. ( 285.8) J K
DH 44.0 kJ@25 C
o o

102
The Temperature
Dependence of Spontaneity

assume DS @ BP DS 0
rxn

DS 0
rxn S 0
H 2O g S 0
H 2O

DS 0
rxn 188.7 69.91 J K
DS 0
rxn 118.8 J K or 0.1188 kJ K
103
The Temperature
Dependence of Spontaneity

DH DH o
44.0 kJ
T= o 370 K
DS DS 0.1188 kJ K
o
370 K-273 K= 97 C

104
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%!!

105
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?
1 acre = 43,460 ft2

106
Synthesis Question
1 in 2.54 cm 1 ft 30.5 cm
1 ft 30.5 cm
2 2
930 cm 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
107
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
DH vaporization of water 44.0 kJ
mol
heat sun must supply 5.71106 mol 44.0 kJ mol

2.51108 kJ 108
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 earths age. Then Rutherford looked at Kelvin
and told him that his method of determining the
earths age based upon how long it would take the
earth to cool from molten rock to its present cool,
solid form
109
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 Kelvins
calculation so far off?

110
 End of Chapter 6
Fireworks are beautiful exothermic
chemical reactions.

111