CHAPTER 10

CHEMICAL THERMODYNAMICS

CONCEPT MAP

LEARNING COMPETENCIES

The learners:

1. Predict the spontaneity of a process on entropy.

2. Determine whether entropy increases or decreases if the following are change:
temperature, phase, number of particles.
3. Explain the second law of thermodynamics and its significance.
4. Use Gibbs free energy to determine the direction of a reaction.
5. Explain the energy changes during chemical reactions
6. Distinguish between exothermic and endothermic processes
7. Explain the first law of thermodynamics
8. Explain enthalpy of a reaction.
9. Write the thermochemical equation for a chemical reaction
10. Calculate the change in enthalpy of a given reaction using Hess Law
11. Do exercises on thermochemical calculations
12. Determine the heat of neutralization of an acid.
THERMODYNAMICS

Thermodynamics let us predict whether a process will occur but gives no

information about the amount of time required for the process.
Figure 16.2: The rate of reaction depends on the pathway from reactants to products; this
is the domain of kinetics. Thermodynamics tells us whether a reaction is spontaneous
based only on the properties of the reactants and products. The predictions of
thermodynamics do not require knowledge of the pathway between reactants and
products.

SPONTANEITY
 Spontaneous: “Occurring without outside intervention.
 A reaction or change of state is said to be spontaneous if it is thermodynamically
allowed.
 For chemistry, prediction of spontaneity is a major goal of thermodynamics.

FACTORS AFFECTING SPONTANEITY

 Energy or Enthalpy: ∆U or ∆H
-Not good predictor. Both endothermic and exothermic reaction can occur.
 Temperature
- Some processes are spontaneous only at certain temperature.
SPONTANEOUS PROCESSES & ENTROPY
 A spontaneous process is a physical or chemical change that occurs by itself.
Examples include:
A rock at the top of hill rolls down.
Heat flows from a hot object to a cold
An iron objects rust in moist air.
 These processes occur without requiring an outside force and continue until
equilibrium reached.

ENTROPY
 Entropy (S) is a thermodynamic state function which can be described qualitatively
as a measure of the amount of disorder present in a system.
 From a chemical perspective, we usually mean molecular disorder.
 Increases in the entropy of a system are usually (not always) accompanied by the
flow of the heat.
 Entropy is a substance depends on physical state. 𝑆𝑔𝑎𝑠 > 𝑆𝑙𝑖𝑞𝑢𝑖𝑑 > 𝑆𝑠𝑜𝑙𝑖𝑑

Solid: Only a few “allowed” positions, molecules or atoms close together

Gas: Many allowed positions, molecules are far apart.
Formula for entropy
∆𝑆 = ∆𝑆 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡) − ∆𝑆 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
SECOND LAW OF THERMODYNAMICS
 Entropy change of the system dos not correctly predicts spontaneity.
 One correct statement of the second law of thermodynamics is:
“The entropy of the universe is always increasing.”
 In equation form, this is:

∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 > 0. Where ∆𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠

 The impact of the transfer of a quantity of heat energy to the surroundings will be
greater when the temperature is low
 For a given reaction, the sign of) 𝑆𝑠𝑢𝑟𝑟 depends on whether) 𝐻𝑠𝑦𝑠 is + or the heat
energy transferred to the surroundings will have the opposite sign!
 The magnitude of) 𝑆𝑠𝑢𝑟𝑟 will depend on the temperature as well as the
magnitude of) 𝐻𝑠𝑦𝑠

GIBBS FREE ENERGY

What’s “free” about Gibbs free energy?
 The change in free energy for a process equals the maximum work that can be
done by the system on the surroundings in a spontaneous process occurring at
constant temperature and pressure. DG = wmax

Example:
What is the maximum work that can be performed by the combustion of 25.0 g of
methanol (CH3OH)?
Step 1: Write a balanced equation. Gibbs Free Energy
Step 2: Calculate 𝐷𝐺𝑟𝑥𝑛
Step 3: Calculate the 𝐷𝐺 for the mass used in the reaction.
You should be able to write a balanced equation for the combustion of an organic
compound or a metal.
 Organic compounds: NOT BALANCE
 Metals: CnHm + O2 CO2 + H2O CxHyON + O2 CO2 + H2O Metal + O2 Metal
oxide
NOT BALANCE
You can use the signs (positive or negative) of 𝐷𝐻 and 𝐷𝑆 to predict whether a
reaction (or process) will be:
 Spontaneous at all temperatures
 Spontaneous only at high temperatures
 Spontaneous only at low temperatures
 Non-spontaneous at all temperatures

The sign of DG (and therefore the spontaneity of the reaction) will depend on.
 The sign of 𝐷𝐻 and 𝐷𝑆
 Relative magnitude of the enthalpy and the entropy terms.
In some cases, the temperature will impact the spontaneity of a reaction.
 HIGHLIGHTS/SUMMARY
 A spontaneous process occurs without the need for a continual input of
energy from some external source, while a nonspontaneous process
requires such.
 Entropy (S) is a state function whose value increases with an increase in
the number of available microstates. For a given system, the greater the
number of microstates, the higher the entropy. During a spontaneous
process, the entropy of the universe increases.
 The greater the molecular motion of a system, the greater the number of
possible microstates and the higher the entropy. A perfectly ordered system
with only a single microstate available to it would have an entropy of zero.
 We can predict whether a reaction will occur spontaneously by combining
the entropy, enthalpy, and temperature of a system in a new state function
called Gibbs free energy (G).
 The change in free energy (ΔG) is the difference between the heat released
during a process and the heat released for the same process occurring in a
reversible manner. If a system is at equilibrium, ΔG = 0. If the process is
spontaneous, ΔG < 0. If the process is not spontaneous as written.
 For a reversible process (with no external work), the change in free energy
can be expressed in terms of volume, pressure, entropy, and temperature.
If ΔG° < 0, then K > 1, and products are favored over reactants. If ΔG° > 0,
then K < 1, and reactants are favored over products. If ΔG° = 0, then K = 1,
and the system is at equilibrium.

CHAPTER ASSESSMENT
1. A thermodynamic state function is _______.
A. A quantity which depends upon temperature only.
B. A quantity which determines pressure-volume work.
C. A quantity which is independent of path.
D. A quantity which determines heat changes.

2: Which of the following is a correct condition for adiabatic condition to occur.

A. q = 0
B. w = 0
C. ΔP = 0
D. ΔT=0

3. The value of enthalpy for all elements in standard state is _____.

A. Zero
B. < 0
C. Different for every element
D. Unity

4: For combustion of methane ΔUΘ is – Y kJmol−1. Then value of ΔHΘ is ____.

A. > ΔUΘ
B. = ΔUΘ
C. = 0
D. < ΔUΘ
5. For, Methane, di-hydrogen and and graphite the enthalpy of combustion at 298K are
given -890.3kJ mol−1, -285.8kJmol−1 and -393.5kJmol−1 respectively. Find the enthalpy
of formation of Methane gas?
A. -52.27kJmol−1
B. 52kJmol−1
C. +74.8kJmol−1
D. -74.8kJmol−1

6. A reaction, X + Y à U + V + q is having a +ve entropy change. Then the reaction ____.

A. will be possible at low temperature only
B. will be possible at high temperature only
C. will be possible at any temperature
D. won’t be possible at any temperature

7. In the process, system absorbs 801 J and work done by the system is 594 J.
Find ΔU for the given process.

8. The reaction given below was done in bomb calorimeter, and at 298K we get, ΔU = -
753.7 kJ mol−1. Find ΔH at 298K.
NH2CN(g) +3/2O2(g) à N2(g) + CO2(g) + H2O(l)

9. Calculate the heat (in kJ) required for 50.0 g aluminum to raise the temperature
from 45∘Cto65∘C. For aluminum molar heat capacity is 24 Jmol−1K−1

10. Calculate ΔH for transformation of 1 mole of water into ice from10∘Cto(−10)∘C.. Δfus
H=6.03kJmol−1at10∘C.
Cp[H2O(l)]=75.3Jmol−1K−1
Cp[H2O(s)]=36.8Jmol−1K−1

11. Enthalpies of formation for CO2(g), CO(g), N2O4(g), N2O(g) are -393kJmol−1,-
110kJmol−1, 9.7kJmol−1and 81kJmol−1 respectively. Then, ΔrH = _____.
N2O4(g) + 3CO(g) à N2O(g) + 3 CO2(g)

12. Enthalpy of combustion of C to CO2 is -393.5 kJmol−1. Determine the heat released
on the formation of 37.2g of CO2 from dioxygen and carbon.

13. N2(g) + 3H2(g) à 2NH3(g) ; ΔrHΘ = -92.4 kJmol−1

Standard Enthalpy for formation of ammonia gas is _____.

14. Determine Standard Enthalpy of formation for CH3OH(l) from the data given below:
CH3OH(l) + (3/2)O2(g) à CO2(g) + 2H2O(l); ΔrHΘ = -726 kJmol−1
C(g) + O2(g) à CO2(g); ΔcHΘ = -393 kJmol−1
H2(g) + (1/2)O2(g) à H2O(l); ΔfHΘ = -286 kJmol−1
15. Calculate ΔH for the following process CCl4(g) à C(g) + 4Cl(g) and determine the
value of bond enthalpy for C-Cl in CCl4(g).
ΔvapHΘ (CCl4) = 30.5 kJmol−1.
ΔfHΘ (CCl4) = -135.5 kJmol−1.
ΔaHΘ (C) = 715 kJmol−1,
ΔaHΘ is a enthalpy of atomisation
ΔaHΘ (Cl2) = 242 kJmol−1.

16. ΔU = 0 for isolated system, then what will be ΔU?

17. Following reaction takes place at 298K, 2X + Y à Z

ΔH = 400 kJmol−1
ΔH = 0.2kJmol−1K−1
Find the temperature at which the reaction become spontaneous
considering ΔS and ΔH to be constant over the entire temperature range?

18. 2Cl(g) à Cl2(g)

In above reaction what can be the sign for ΔS and ΔH?

19. 2X(g) + Y(g) à 2D(g)

ΔUΘ = -10.5 kJ and ΔSΘ = -44.1JK−1
Determine ΔGΘ for the given reaction, and predict that whether given reaction can occur
spontaneously or not.

20. Find the value of ΔGΘ for the reaction, if equilibrium is given 10. given that T = 300K
and R = 8.314×10−3kJK−1mol−1.
KEY TO CORRECTION
1. A thermodynamic state function is _______.
A. A quantity which depends upon temperature only.
B. A quantity which determines pressure-volume work.
C. A quantity which is independent of path.
D. A quantity which determines heat changes.

Answer:
C. A quantity which is independent of path.
Reason:
Functions like pressure, volume and temperature depends on the state of the system only
and not on the path.

2: Which of the following is a correct condition for adiabatic condition to occur.

A. q = 0
B. w = 0
C. Δp=0
D. ΔT=0

Answer:
A. q = 0
Reason:
For an adiabatic process heat transfer is zero, i.e. q = 0.

3. The value of enthalpy for all elements in standard state is _____.

A. Zero
B. < 0
C. Different for every element
D. Unity

Answer:
A. Zero

4: For combustion of methane ΔUΘ is – Y kJmol−1. Then value of ΔHΘ is ____.

A. > ΔUΘ
B. = ΔUΘ
C. = 0
D. < ΔUΘ

Answer:
D < ΔUΘ
Reason:
ΔHΘ=ΔUΘ+ΔngRT ; ΔUΘ = – Y kJmol−1,
ΔHΘ=(–Y)+ΔngRT⇒ΔHΘ<ΔUΘ

5. For, Methane, di-hydrogen and and graphite the enthalpy of combustion at 298K are
given -890.3kJ mol−1, -285.8kJmol−1 and -393.5kJmol−1 respectively. Find the enthalpy
of formation of Methane gas?
A. -52.27kJmol−1
B. 52kJmol−1
C. +74.8kJmol−1
D. -74.8kJmol−1

Answer:
D. -74.8kJmol−1
à CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
ΔH=−890.3kJmol−1
à C(s) + O2(g) → CO2(g)
ΔH=−393.5kJmol−1
à 2H2(g) + O2(g) → 2H2O(g)
ΔH=−285.8kJmol−1
à C(s) + 2H2(g) → CH4(g)
ΔfHCH4 = ΔcHc + 2ΔfHH2 – ΔfHCO2
= [ -393.5 +2(-285.8) – (-890.3)] kJmol−1
= -74.8kJmol−1

6. A reaction, X + Y à U + V + q is having a +ve entropy change. Then the reaction ____.

A. will be possible at low temperature only
B. will be possible at high temperature only
C. will be possible at any temperature
D. won’t be possible at any temperature

Answer:
C. will be possible at any temperature
ΔG should be –ve, for spontaneous reaction to occur
ΔG = ΔH – TΔS
As per given in question,
ΔH is –ve ( as heat is evolved)
ΔS is +ve
Therefore, ΔG is negative
So, the reaction will be possible at any temperature.

7. In the process, system absorbs 801 J and work done by the system is 594 J. Find ΔU for
the given process.

Answer:
As per Thermodynamics 1st law,
ΔU = q + W(i);
ΔU internal energy = heat
W = work done
W = -594 J (work done by system)
q = +801 J (+ve as heat is absorbed)
Now,
ΔU = 801 + (-594)
ΔU = 207 J

8. The reaction given below was done in bomb calorimeter, and at 298K we get, ΔU = -
753.7 kJ mol−1. Find ΔH at 298K.
NH2CN(g) +3/2O2(g) à N2(g) + CO2(g) + H2O(l)
Answer:
ΔH is given by,
ΔH=ΔU+ΔngRT………………(1)
Δng = change in number of moles
ΔU = change in internal energy
Here,
Δng=∑ng(product)–∑ng(reactant)
= (2 – 2.5) moles
Δng = -0.5 moles
Here,
T =298K
ΔU = -753.7 kJmol−1
R = 8.314×10−3kJmol−1K−1
Now, from (1)
ΔH=(−753.7kJmol−1)+(−0.5mol)(298K)(8.314×10−3kJmol−1K−1)
= -753.7 – 1.2
ΔH = -754.9 kJmol−1

9. Calculate the heat (in kJ) required for 50.0 g aluminum to raise the temperature
from 45∘Cto65∘C. For aluminum molar heat capacity is 24 Jmol−1K−1

Answer:
Expression of heat (q),
𝑞 = 𝑚𝐶𝑃𝛥𝑇;………………….(a)
𝛥𝑇 = Change in temperature
𝑐 = molar heat capacity
m = mass of substance
From (a)
q=(5027mol)(24mol−1K−1)(20K)
q = 888.88 J q

10. Calculate ΔH for transformation of 1 mole of water into ice

from10∘Cto(−10)∘C.. ΔfusH=6.03kJmol−1at10∘C.
Cp[H2O(l)]=75.3Jmol−1K−1
Cp[H2O(s)]=36.8Jmol−1K−1

Answer:
ΔHtotal = sum of the changes given below:
A. Energy change that occurs during transformation of 1 mole of water from 10∘Cto0∘C.
B. Energy change that occurs during transformation of 1 mole of water at 0∘C to 1 mole
of ice at 0∘C.
C. Energy change that occurs during transformation of 1 mole of ice from 0∘C to (−10)∘C.
ΔHtotal=Cp[H2OCl]ΔT+ΔHfreezingCp[H2Os]ΔT
= (75.3 Jmol−1K−1)(0 – 10)K + (-6.03*1000 Jmol−1(-10-0)K
= -753 Jmol−1 – 6030Jmol−1 – 368Jmol−1
= -7151 Jmol−1
= -7.151kJmol−1
Thus, the required change in enthalpy for given transformation is -7.151kJmol−1.
11. Enthalpies of formation for CO2(g), CO(g), N2O4(g), N2O(g) are -393kJmol−1,-
110kJmol−1, 9.7kJmol−1and 81kJmol−1 respectively. Then, ΔrH = _____.
N2O4(g) + 3CO(g) à N2O(g) + 3 CO2(g)

Answer:
“ΔrH for any reaction is defined as the difference between ΔfH value of products
and ΔfH value of reactants.”
ΔrH=∑ΔfH(products)–∑ΔfH(reactants)
Now, for
N2O4(g) + 3CO(g) à N2O(g) + 3 CO2(g)
ΔrH=[(ΔfH(N2O)+(3ΔfH(CO2))–(ΔfH(N2O4)+3ΔfH(CO))]
Now, substituting the given values in the above equation, we get:
ΔrH = [{81kJmol−1 + 3(-393) kJmol−1} – {9.7kJmol−1 + 3(-110) kJmol−1}] ΔrH = -
777.7 kJmol−1

12. Enthalpy of combustion of C to CO2 is -393.5 kJmol−1. Determine the heat released
on the formation of 37.2g of CO2 from dioxygen and carbon.

Answer:
Formation of carbon dioxide from di-oxygen and carbon gas is given as:
C(s) + O2(g) à CO2(g); ΔfH = -393.5 kJmol−1
1 mole CO2 = 44g
Heat released during formation of 44g CO2 = -393.5 kJmol−1
Therefore, heat released during formation of 37.2g of CO2 can be calculated as
= −393.5kJmol−144g×37.2g
= -332.69 kJmol−1

13. N2(g) + 3H2(g) à 2NH3(g) ; ΔrHΘ = -92.4 kJmol−1

Standard Enthalpy for formation of ammonia gas is _____.

Answer:
“Standard enthalpy of formation of a compound is the enthalpy that takes place during the
formation of 1 mole of a substance in its standard form, from its constituent elements in
their standard state.”
Dividing the chemical equation given in the question by 2, we get
(0.5)N2(g) + (1.5)H2(g) à 2NH3(g)
Therefore, Standard Enthalpy for formation of ammonia gas
= (0.5) ΔrHΘ
= (0.5)(-92.4kJmol−1)
= -46.2kJmol−1

14. Determine Standard Enthalpy of formation for CH3OH(l) from the data given below:
CH3OH(l) + (3/2)O2(g) à CO2(g) + 2H2O(l); ΔrHΘ = -726 kJmol−1
C(g) + O2(g) à CO2(g); ΔcHΘ = -393 kJmol−1
H2(g) + (1/2)O2(g) à H2O(l); ΔfHΘ = -286 kJmol−1

Answer:
C(s) + 2H2O(g) + (1/2)O2(g) à CH3OH(l) …………………………(i)
CH3OH(l) can be obtained as follows,
ΔfHΘ [CH3OH(l)] = ΔcHΘ
2ΔfHΘ – ΔrHΘ
= (-393 kJmol−1) +2(-286kJmol−1) – (-726kJmol−1)
= (-393 – 572 + 726) kJmol−1
= -239kJmol−1
Thus, ΔfHΘ [CH3OH(l)] = -239kJmol−1

15. Calculate ΔH for the following process CCl4(g) à C(g) + 4Cl(g) and determine the
value of bond enthalpy for C-Cl in CCl4(g).
ΔvapHΘ (CCl4) = 30.5 kJmol−1.
ΔfHΘ (CCl4) = -135.5 kJmol−1.
ΔaHΘ (C) = 715 kJmol−1,
ΔaHΘ is a enthalpy of atomisation
ΔaHΘ (Cl2) = 242 kJmol−1.

Answer:
“ The chemical equations implying to the given values of enthalpies” are:
(1) CCl4(l) à CCl4(g) ; ΔvapHΘ = 30.5 kJmol−1
(2) C(s) à C(g) ΔaHΘ = 715 kJmol−1
(3) Cl2(g) à 2Cl(g) ; ΔaHΘ = 242 kJmol−1
(4) C(g) + 4Cl(g) à CCl4(g); ΔfHΘ = -135.5 kJmol−1 ΔH for the process CCl4(g) à C(g) +
4Cl(g) can be measured as:
ΔH=ΔaHΘ(C)+2ΔaHΘ(Cl2)–ΔvapHΘ–ΔfH
= (715kJmol−1) + 2(kJmol−1) – (30.5kJmol−1) – (-135.5kJmol−1)
Therefore, H=1304kJmol−1
The value of bond enthalpy for C-Cl in CCl4(g)
= 13044kJmol−1
= 326 kJmol−1

16. ΔU = 0 for isolated system, then what will be ΔU?

Answer:
ΔU is positive ; ΔU > 0.
As, ΔU = 0 thenΔS will be +ve, as a result reaction will be spontaneous.

17. Following reaction takes place at 298K, 2X + Y à Z

ΔH = 400 kJmol−1
ΔH = 0.2kJmol−1K−1
Find the temperature at which the reaction become spontaneous
considering ΔS and ΔH to be constant over the entire temperature range?

Answer:
Now,
ΔG=ΔH–TΔS
Let, the given reaction is at equilibrium, then ΔT will be:
T = (ΔH–ΔG)1ΔS ΔHΔS; (ΔG = 0 at equilibrium)
= 400kJmol−1/0.2kJmol−1K−1
Therefore, T = 2000K
Thus, for the spontaneous, ΔG must be –ve and T > 2000K.

18. 2Cl(g) à Cl2(g)

In above reaction what can be the sign for ΔS and ΔH?
Answer:
ΔS and ΔH are having negative sign.
The reaction given in the question represents the formation of Cl molecule from Cl atoms.
As the formation of bond takes place in the given reaction. So, energy is released.
So, ΔH is negative.
Also, 2 moles of Chlorine atoms is having more randomness than 1 mole of chlorine
molecule. So, the spontaneity is decreased. Thus, ΔS is negative.

19. 2X(g) + Y(g) à 2D(g)

ΔUΘ = -10.5 kJ and ΔSΘ = -44.1JK−1
Determine ΔGΘ for the given reaction, and predict that whether given reaction can occur
spontaneously or not.

Answer:
2X(g) + Y(g) à 2D(g)
Δng = 2 – 3
= -1 mole
Putting value of ΔUΘ in expression of ΔH:
ΔHΘ=ΔUΘ+ΔngRT
= (-10.5KJ) – (-1)( 8.314×10−3kJK−1mol−1)(298K)
= -10.5kJ -2.48kJ
ΔHΘ = -12.98kJ
Putting value of ΔSΘ and ΔHΘ in expression of ΔGΘ:
ΔGΘ=ΔHΘ–TΔSΘ
= -12.98kJ –(298K)(-44.1JK−1)
= -12.98kJ +13.14kJ
ΔGΘ = 0.16kJ
As, ΔGΘ is positive, the reaction won’t occur spontaneously.

20. Find the value of ΔGΘ for the reaction, if equilibrium is given 10. given that T = 300K
and R = 8.314×10−3kJK−1mol−1.

Answer:
Now,
ΔGΘ = −2.303RTlogeq
= (2.303)( 8.314×10−3kJK−1mol−1)(300K) log10
= -5744.14Jmol−1
-5.744kJmol−1

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