Thermodynamics

Chapter 18

1
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Spontaneous Physical and Chemical Processes
• A waterfall runs downhill
• A lump of sugar dissolves in a cup of coffee
• At 1 atm, water freezes below 0 oC and ice melts above 0 oC
• Heat flows from a hotter object to a colder object
• A gas expands in an evacuated bulb
• Iron exposed to oxygen and
water forms rust
spontaneous

nonspontaneous

2
 spontaneous

nonspontaneous

3
Does a decrease in enthalpy mean a reaction proceeds
spontaneously?

Spontaneous reactions

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H0 = -890.4 kJ/mol

H+ (aq) + OH- (aq) H2O (l) H0 = -56.2 kJ/mol

H2O (s) H2O (l) H0 = 6.01 kJ/mol

H2O
NH4NO3 (s) NH4+(aq) + NO3- (aq) H0 = 25 kJ/mol

4
Exotermicity favors spontaneous reaction but does not
guarantee it.

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Entropy (S) is a measure of the randomness or disorder of a
system.

order S disorder S

S = Sf - Si
If the change from initial to final results in an increase in randomness

Sf > Si S > 0

For any substance, the solid state is more ordered than the
liquid state and the liquid state is more ordered than gas
state.
Ssolid < Sliquid << Sgas

H2O (s) H2O (l) S > 0 6

 Entropy

W = number of microstates
S = k ln W
S = Sf - Si
Wf
S = k ln
Wi

Wf > Wi then S > 0

Wf < Wi then S < 0

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Processes that lead to an increase in entropy (S > 0)

8
Example: Br2(l) Br2(g) Example: I2(s) I2(g)

S > 0 S > 0

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 Entropy

State functions are properties that are determined by the state

of the system, regardless of how that condition was achieved.
Examples:
energy, enthalpy, pressure, volume, temperature, entropy
Review

Potential energy of hiker 1 and hiker 2

is the same even though they took
10
different paths.
standard molar entropy the
entropy content of one mole of
substance under a standard
state

The entropy of a pure crystalline

structure can be 0 J/mol* K only
at 0 K

11
Example 18.1
Predict whether the entropy change is greater or less than
zero for each of the following processes:

(a) freezing ethanol

(b) evaporating a beaker of liquid bromine at room

temperature

(c) dissolving glucose in water

(d) cooling nitrogen gas from 80°C to 20°C

12
Example 18.1

Strategy
To determine the entropy change in each case, we examine
whether the number of microstates of the system increases or
decreases. The sign of ΔS will be positive if there is an increase
in the number of microstates and negative if the number of
microstates decreases.

Solution
(a) Upon freezing, the ethanol molecules are held rigid in
position. This phase transition reduces the number of
microstates and therefore the entropy decreases; that is,
ΔS < 0.

13
Example 18.1

(b) Evaporating bromine increases the number of microstates

because the Br2 molecules can occupy many more positions
in nearly empty space. Therefore, ΔS > 0.

(c) Glucose is a nonelectrolyte. The solution process leads to a

greater dispersal of matter due to the mixing of glucose and
water molecules so we expect ΔS > 0.

(d) The cooling process decreases various molecular motions.

This leads to a decrease in microstates and so ΔS < 0.

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• Which species will have the greatest absolute
entropy at 25°C?
• A) Ne(g) B) C H (g) C) H O(l) D) C H OH(l)
2 2 2 2 5 E)
C4H10(g)
• Ans: E

15
First Law of Thermodynamics

Energy can be converted from one form to another but

energy cannot be created or destroyed.

Second Law of Thermodynamics

The entropy of the universe increases in a spontaneous

process and remains unchanged in an equilibrium process.

Spontaneous process: Suniv = Ssys + Ssurr > 0

Equilibrium process: Suniv = Ssys + Ssurr = 0

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 Entropy Changes in the System (Ssys)
The standard entropy of reaction (S0rxn) is the entropy
change for a reaction carried out at 1 atm and 250C.

aA + bB cC + dD

S0rxn = [ cS0(C) + dS0(D) ] - [ aS0(A) + bS0(B) ]

S0rxn =  nS0(products) -  mS0(reactants)

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Example 18.2

From the standard entropy values in Appendix 2, calculate the

standard entropy changes for the following reactions at 25°C.

(a) CaCO3(s) CaO(s) + CO2(g)

(b) N2(g) + 3H2(g) 2NH3(g)

(c) H2(g) + Cl2(g) 2HCl(g)

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Example 18.2

Strategy

To calculate the standard entropy of a reaction, we look up the

standard entropies of reactants and products in Appendix 2 and
apply Equation (18.7). As in the calculation of enthalpy of
reaction [see Equation (6.18)], the stoichiometric coefficients
have no units, so ΔS°rxn is expressed in units of J/K·mol.

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Example 18.2
Solution
CaCO3(s) CaO(s) + CO2(g)
(a) ΔS°rxn = [S°(CaO) + S°(CO2)] - [S°(CaCO3)]
= [(39.8 J/K·mol) + (213.6 J/K·mol)] - (92.9 /K·mol)
= 160.5 J/K·mol

Thus, when 1 mole of CaCO3 decomposes to form 1 mole of

CaO and 1 mole of gaseous CO2, there is an increase in entropy
equal to 160.5 J/K·mol.

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Example 18.2
N2(g) + 3H2(g) 2NH3(g)

(b) ΔS°rxn = [2S°(NH3)] - [S°(N2) + 3S°(H2)]

= (2)(193 J/K·mol) - [(192 J/K·mol) + (3)(131 J/K·mol)]
= -199 J/K·mol

This result shows that when 1 mole of gaseous nitrogen reacts

with 3 moles of gaseous hydrogen to form 2 moles of gaseous
ammonia, there is a decrease in entropy equal to -199 J/K·mol.

21
Example

• 1903 年，合成氨反應才由德國科學家弗里茨·哈伯在 1020℃ 常壓條件下極微量的

0.005% 氨產生。弗里茨·哈伯提出通過封閉流程和循環操作工藝轉化為氨。在哈伯過程發
現之前，氨一直難以大規模生產。三五計劃期間瀋陽開原合成氨廠
• 1908 年 2 月，弗里茨·哈伯與巴斯夫公司達成協議。 1909 年，德國巴斯夫公司的卡爾
·博施發現 Os對合成氨的高效催化。
• 1909 年 7 月 2 日哈伯領導的研究小組首次用金屬鋨粉末催化劑，在高溫高壓設備中成功
地生產出 90g 氨。巴斯夫公司的 Alwin Mittasche 提出合成氨的催化劑是多組分體
系，經過一年半對 2500 種催化劑的 6500 次試驗，最終發現最高效的含有鉀 - 氧化鋁
助劑的鐵催化劑，並沿用至今。

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Example
• 哈伯法（也稱哈伯 - 博施法，也稱 Haber-Bosch process 或 Fritz-
Haber Process ）是通過氮氣及氫氣產生氨氣（ NH3 ）的過程。
• 氮氣及氫氣在 500 個大氣氣壓及攝氏 500 度，通過一個鐵催化劑（ Fe ），會發生化學
作用，產生氨氣。在這個情況下，產量一般是 10-20% 。
• ΔHo, 反應焓變為 -92.4 kJ/mol 。
• 選擇較高溫的條件是為了有較高反應速率，但因為正向反應是放熱反應，在此條件下平衡後的產
率反而較低溫時為低。
• 氮是限制植物生長的一個關鍵的礦質營養。雖然大氣中的空氣是 78 ％的氮氣，但大氣中的氮
是不可用的營養，因為氮分子以強大的三鍵結合在一起。氮必須被「固定」，即通過自然或人為
的過程轉換成某種生物可利用的形式。

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Example

• H2 is very potential and appropriate to be used as both

energy carrier and storage.

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Example 18.2

H2(g) + Cl2(g) 2HCl(g)

(c) ΔS°rxn = [2S°(HCl)] - [S°(H2) + S°(Cl2)]

= (2)(187 J/K·mol) - [(131 J/K·mol) + (223 J/K·mol)]
= 20 J/K·mol

Thus, the formation of 2 moles of gaseous HCl from 1 mole of

gaseous H2 and 1 mole of gaseous Cl2 results in a small
increase in entropy equal to 20 J/K·mol.

Comment The ΔS°rxn values all apply to the system.

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 Example
15. Sulfur can be separated from lead in the mineral galena, PbS(s), by “roasting” the
ore in the presence of oxygen as shown in the following reaction:
2PbS(s) + 3O2(g) 2PbO(s) + 2SO2(g)
Calculate DS° for this reaction using the
thermodynamic data provided below.

A) –410 J/K·mol D) 21.8 J/K·mol

B) –161.5 J/K·mol E) 43.5 J/K·mol
C) –47.7 J/K·mol
Ans: B
S°(J/K·mol)
PbS(s) 91.2
O2(g) 205.0
PbO(s) 69.45
SO2(g) 248.5

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 Entropy Changes in the System (Ssys)
When gases are produced (or consumed)

• If a reaction produces more gas molecules than it

consumes, S0 > 0.
• If the total number of gas molecules diminishes, S0 < 0.
• If there is no net change in the total number of gas
molecules, then S0 may be positive or negative BUT
S0 will be a small number.

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Example 18.3
Predict whether the entropy change of the system in each of the
following reactions is positive or negative.

(a) 2H2(g) + O2(g) 2H2O(l)

(b) NH4Cl(s) NH3(g) + HCl(g)

(c) H2(g) + Br2(g) 2HBr(g)

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Example 18.3

Solution

(a) Two reactant molecules combine to form one product

molecule. Even though H2O is a more complex molecule
than either H2 and O2, the fact that there is a net decrease
of one molecule and gases are converted to liquid ensures
that the number of microstates will be diminished and hence
ΔS° is negative.

(b) A solid is converted to two gaseous products. Therefore,

ΔS° is positive.

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Example 18.3
(c) The same number of molecules is involved in the reactants
as in the product. Furthermore, all molecules are
diatomic and therefore of similar complexity. As a
result, we cannot predict the sign of ΔS°, but we know
that the change must be quite small in magnitude.

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Example

• Without reference to a table, arrange these reactions

according to increasing S.
• 1. CH4(g) + H2O(g)  CO(g) + 3H2(g)
• 2. C(s) + O2(g)  CO2(g)
• 3. H2O2(l)  H2O(l) + 1/2O2(g)
• A) 1 < 3 < 2 B) 2 < 3 < 1 C) 2 < 1 < 3
D) 3 < 2 < 1 E) 3 < 1 < 2

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 Entropy Changes in the Surroundings (Ssurr)

Exothermic Process Endothermic Process

Ssurr > 0 Ssurr < 0

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Third Law of Thermodynamics
The entropy of a perfect crystalline substance is zero at the
absolute zero of temperature.

S = k ln W
W=1
S=0

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 Gibbs Free Energy

• Energy availible to do work

 Gibbs Free Energy
Spontaneous process: Suniv = Ssys + Ssurr > 0

Equilibrium process: Suniv = Ssys + Ssurr = 0

For a constant temperature and

constant pressure process:
Gibbs free G = Hsys -TSsys
energy (G)

G < 0 The reaction is spontaneous in the forward direction.

G > 0 The reaction is nonspontaneous as written. The
reaction is spontaneous in the reverse direction.
G = 0 The reaction is at equilibrium.

35
The standard free-energy of reaction (G0rxn) is the free-
energy change for a reaction when it occurs under standard-
state conditions.
aA + bB cC + dD

Grxn
0
= [ cG0f (C) + dG0f (D) ] - [ aG0f (A) + bG0f (B) ]

Grxn
0
=  nG0f (products) -  mG0f (reactants)

Standard free energy of formation (G0f ) is the free-energy

change that occurs when 1 mole of the compound is formed
from its elements in their standard states.

G0f of any element in its stable form is zero.

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37
Example 18.4
Calculate the standard free-energy changes for the following
reactions at 25°C.

(a) CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

(b) 2MgO(s) 2Mg(s) + O2(g)

38
Example 18.4
Solution
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

(a)According to Equation (18.12), we write

ΔG°rxn = [ΔG°f (CO2) + 2ΔG°f (H2O)] - [ΔG°f (CH4) + 2ΔG°f (O2)]

We insert the appropriate values from Appendix 2:

ΔG°rxn =[(-394.4 kJ/mol) + (2)(-237.2 kJ/mol)] -

[(-50.8 kJ/mol) + (2) (0 kJ/mol)]

= -818.0 kJ/mol
39
Example 18.4

(b) The equation is

2MgO(s) 2Mg(s) + O2(g)

ΔG°rxn = [2ΔG°f (Mg) + ΔG°f (O2)] - [2ΔG°f (MgO)]

From data in Appendix 2 we write

ΔG°rxn = [(2)(0 kJ/mol) + (0 kJ/mol)] - [(2)(-569.6 kJ/mol)]

= 1139 kJ/mol

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G = H - TS

41
A reaction has a positive enthalpy change and a
positive entropy change. Which of the
following will make it more spontaneous?
A) Adding a catalyst.
B) Increasing the temperature.
C) Decreasing the temperature.
D) None of the above.

42
 Temperature and Spontaneity of Chemical Reactions

CaCO3 (s) CaO (s) + CO2 (g)

Equilibrium Pressure of CO2

H0 = 177.8 kJ/mol

S0 = 160.5 J/K·mol
G0 = H0 – TS0
At 25 oC, G0 = 130.0 kJ/mol
G0 = 0 at 835 oC

43
44
 CaCO3 (s) CaO (s) + CO2 (g)
• CaO ( 石灰 )+H2O Ca(OH)2
• Ca(OH)2+CO2 CaCO3+H2O
•

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46
G0 =  RT lnK

47
Example 18.6
Using data listed in Appendix 2, calculate the equilibrium
constant (KP) for the following reaction at 25°C:

2H2O(l) 2H2(g) + O2(g)

48
Example 18.6
Solution According to Equation (18.12),

ΔG°rxn = [2ΔG°f(H2) + ΔG°f(O2)] - [2ΔG°f(H2O)]

= [(2)(0 kJ/mol) + (0 kJ/mol)] - [(2)(-237.2 kJ/mol)]
= 474.4 kJ/mol

Using Equation (18.14)

o
ΔGrxn = -RTlnK p
1000 J
474.4 kJ/mol × = -(8.314J/K mol)(298 K)lnK p
1 kJ
lnK p = -191.5
K p  e  191.5 = 7 × 10-84
49
Example 18.6
Comment

This extremely small equilibrium constant is consistent with the

fact that water does not spontaneously decompose into
hydrogen and oxygen gases at 25°C. Thus, a large positive
ΔG° favors reactants over products at equilibrium.

50
Example 18.7
In Chapter 17 we discussed the solubility product of slightly
soluble substances. Using the solubility product of silver
chloride at 25°C (1.6 x 10-10), calculate ΔG° for the process

AgCl(s) Ag+(aq) + Cl-(aq)

51
Example 18.7
Solution The solubility equilibrium for AgCl is

AgCl(s) Ag+(aq) + Cl-(aq)

Ksp = [Ag+][Cl-] = 1.6 x 10-10

Using Equation (18.14) we obtain

ΔG° = -(8.314 J/K·mol) (298 K) ln (1.6 x 10-10)

= 5.6 x 104 J/mol
= 56 kJ/mol

Check The large, positive ΔG° indicates that AgCl is slightly

soluble and that the equilibrium lies mostly to the left.
52
 Gibbs Free Energy and Chemical Equilibrium

G = G0 + RT lnQ

R is the gas constant (8.314 J/K•mol)

T is the absolute temperature (K)

Q is the reaction quotient

At Equilibrium

G = 0 Q=K

0 = G0 + RT lnK
G0 =  RT lnK

53
Example 18.8
The equilibrium constant (KP) for the reaction

N2O4(g) 2NO2(g)

is 0.113 at 298 K, which corresponds to a standard free-energy

change of 5.40 kJ/mol. In a certain experiment, the initial
pressures are PNO = 0.122 atm and PN O = 0.453 atm.
2 2 4

Calculate ΔG for the reaction at these pressures and predict the

direction of the net reaction toward equilibrium.

54
Example 18.8
Solution Equation (18.13) can be written as

ΔG = ΔG o + RTlnQp
2
PNO
= ΔG o + RTln 2

PN 2O4

3 (0.122) 2
= 5.40 × 10 J/mol + (8.314J/K mol)(298 K) × ln
0.453
= 5.40 × 103 J/mol - 8.46 × 103 J/mol
= -3.06 × 103J/mol = - 3.06kJ / mol

Because ΔG < 0, the net reaction proceeds from left to right to

reach equilibrium.
55
 Free Energy Versus Extent of Reaction

G0 < 0 G0 > 0

56
Example

G0 < 0 G0 > 0

Note that although ΔG° > 0, the reaction can be made

to favor product formation initially by having a small
concentration (pressure) of the product compared to
that of the reactant. Confirm the prediction by showing
that QP < KP.
• The standard Gibb's free energy change for
a reaction is -50. kJ. If the concentrations
present are such that Q = 10, then the actual
Gibb's free energy change at 298 K is
• A) -55.7 kJ.
• B) -44.3 kJ.
• C) 5654 kJ.
• D) 5754 kJ.
(B)
58
21. A negative sign for G indicates that, at constant T and P,
A) the reaction is exothermic.
B) the reaction is endothermic.
C) the reaction is fast.
D) the reaction is spontaneous.
(E) S must be > 0.
Ans: D

59
A spontaneous reaction
A) has an equilibrium constant greater than 1.
B) has a Gibb's free energy value less than
zero.
C) causes an overall increase in the entropy
of the universe.
D) all of the above (D)

60
The Structure of ATP and ADP in Ionized Forms

61
 Coupled Reactions

Example: Alanine + Glycine Alanylglycine

G0 = +29 kJ K<1

ATP + H2O + Alanine + Glycine ADP + H3PO4 + Alanylglycine

G0 = -2 kJ K>1
62
63
64
Distinction between thermodynamics and kinetics

A high activation energy barrier

very slow in the absence of an enzyme catalyst.

This "kinetic stability" is essential to the role of ATP

and other compounds with ~ bonds.

If ATP would rapidly hydrolyze in the absence of a

catalyst, it could not serve its important roles in energy
metabolism and phosphate transfer.
.

65