Tutorial CHM432

Chapter 2

Thermodynamics

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Q1

Briefly explain the difference between ∆H and ∆E.

• JUN 2016

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Answer Q1
Enthalpy (∆H) is the sum of the internal energy (∆E) of the system plus
the product of the pressure (P) of the gas in the system and its volume
(V). ie: H = E + PV

Internal Energy (∆E) is the total energy contained in the system. It is

the sum of potential and kinetic energy possessed by the system. The
internal energy can be transferred into heat and/or work. ie: E = q + w.

Or:
∆H is heat measured at constant pressure, so ∆H = qp.
∆E is heat measured at constant volume, so ∆E = qv.

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Q2
Consider the following reaction:
2N2O(g) + 3O2(g) ↔ 4NO2(g)
In a reaction mixture, the gases involved in the reaction have the
following partial pressure : N2O(g) = 220 torr, O2(g) = 120 torr, NO2(g)
= 458 torr. This reaction has ∆Go = +0.17 kJ mol-1.
i) Determine whether this reaction has reached the equilibrium stage.
ii) If not, determine the direction of reaction must proceed in order to
reach equilibrium.
• JUN 2016
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 Answer Q2
i) At equilibrium stage, ∆G = 0 and Q = K. Since the value of K is not given, so we
can calculate ∆G.
Using this formula: ∆G = ∆Go + RT ln Q
2N2O(g) + 3O2(g) ↔ 4NO2(g)
Q = (ρNO2)4 = (458)4 = 0.526
(ρN2O)2(ρO2)3 (220)2(120)3

∆G = +0.17 x 103 + (8.314)(298) ln 0.526 = -12.3 kJ mol-1

Since ∆G is not equal to zero, this reaction mixture is not at equilibrium.

ii) Since the forward reaction is spontaneous (∆G= -ve), the forward reaction is
possible to occur and to reach equilibrium; N2O and O2 must react to form NO2.
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Q3

Define state function in thermodynamics with an example.

• DEC 2016

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Answer Q3
State function –
Properties that are determined by the state of the system regardless of
how that condition was achieved.

Example: ∆H, ∆E, ∆T, ∆P, ∆S, ∆G or ∆V.

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Q4
A sample of nitrogen gas expands in volume from 1.6L to 5.4L at
constant temperature.

i) Calculate the work done in joules if the gas expands against a

constant pressure of 0.80 atm.
ii) Calculate the internal energy change of the gas if the expansion
process absorbs 127J of heat from the surroundings.
• DEC 2016

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Answer Q4
i) w= -P∆V
= - (0.80 atm) (5.4L - 1.6L)
= - 3.04 [Link]
= - (3.04 [Link] x 101.3 J/[Link]) = -307.95 J

ii) ∆E = q + w
= (+127 J) + (-307.95 J)
= -180.95 J

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Q5
Calcium oxide (CaO) is an extremely valuable inorganic substance used in steelmaking, production
of calcium metal and paper industry. It is prepared by decomposition of limestone (CaCO3) as shown
in the equation below.
CaCO3(s) ↔ CaO (s) + CO2 (g)
This reaction is reversible and CaO is readily combined with CO2 to form CaCO3.
i) Calculate ∆Ho and ∆So for the reaction at 25oC.
ii) Determine standard free Gibbs energy change for the reaction at 25oC.
iii) Determine the spontaneity of the reaction at 25oC.
[∆Hof CaO (s) = -635.6kJ mol-1, ∆Hof CO2(g) = -395.5kJ mol-1, ∆Hof CaCO3 (s) = -1206.9 kJ mol-1]
[So CaO (s) = 39.8 JK-1 mol-1, So CO2(g) = 213.6 JK-1 mol-1, So CaCO3(s) = 92.9 JK-1 mol-1]
• DEC 2016

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Answer Q5
i) ∆Ho = [(∆HofCaO + ∆HofCO2)] – [∆HofCaCO3]
= [(-635.6 ) + (-393.5)] – [- 1206.9]
= +177.8 kJ mol-1

∆So = [So CaO + SoCO2] - [SoCaCO3]

= [ (39.8) + (213.6)] - [92.9]
= 160 J K-1 mol-1

ii) ∆Go = ∆Ho - T∆So

= (+177.8 kJ mol-1) - (25 + 273 K) (0.160 kJ K-1 mol-1)
= + 130.0 kJ mol-1

iii) Since ∆Go is positive, the forward reaction is not spontaneous.

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Q6
Consider the combustion of 1 mole of propane at 25oC as shown in equation below:
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l)
Table 1: Standard molar properties at 25oC
Substance So (JK-1mol-1) ∆Hof (kJ mol-1) ∆Gof (kJ mol-1)
C3H8 269.9 -103.8 -23.49
O2 205.0 0 0
CO2 213.7 -393.5 -394.4
H2O 69.9 -285.8 -237.8

By referring to Table 1:
i) Calculate the value of entropy change (∆Sorxn) for the reaction.
ii) Calculate the enthalpy change (∆Horxn) for the reaction.
iii) Calculate the value of free Gibbs energy change (∆Gorxn) for the reaction.
iv) Determine whether this reaction is spontaneous or non-spontaneous at 25oC.
• JUL 2017
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Answer Q6
i) ∆Sorxn = ∑ So products - ∑ So reactants
= [(3So CO2 + 4So H2O)] – [(1SoC3H8 + 5SoO2)]
= (3 (213.7) + 4(69.9)) - (1(269.9) + 5(205.0))
= -374.2 J K-1 mol-1 @ -0.3742 kJ K-1 mol-1

ii) ∆Horxn = ∑ ∆Hof products - ∑ ∆Hof reactants

= [(3 (-393.5) + 4(-285.8)] - [1(-103.8) + 5(0)]
= - 2219.9 kJ mol-1

iii) ∆Gorxn = ∆Horxn - T∆Sorxn

= (-2219.9 kJ mol-1) - (25 + 273 K) (- 0.3742 kJ K-1 mol-1)
= - 2108.4 kJ mol-1

iv) Since ∆Go = -ve , therefore this reaction is spontaneous at 25oC.

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Q7

List two factors affecting the value of entropy of the system.

• JUL 2017

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Answer Q7
Choose any two factors:

• Temperature
• Physical State
• Atomic Size
• Molecular Complexity
• Dissolution

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Q8
Identify the sign of the entropy change for the following processes.

i) Water condenses as droplets on a cold windowpane.

ii) Expansion of gas.
• JUL 2017

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Answer Q8

i) Condensation process ; (g) → (l)

∆S = - ve (becomes more order)

ii) Expansion of gas

∆S = + ve (becomes more disorder)

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Q9
Consider the following reactions:

Reaction 1: C(s) + O2(g) → CO2(g)

∆Ho = -393.51kJmol-1, ∆So = 2.86 JK-1mol-1

Reaction 2: 2NO2(g) → N2O4(g)

∆Ho = -57.20kJmol-1, ∆So = -175.83 JK-1mol-1

Compare the temperature dependence of these reactions.

• JUL 2017

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Answer Q9
Reaction 1:
Since ∆Ho and ∆So have opposite sign, therefore reaction 1 has ∆Gorxn =
negative. This indicates that reaction 1 is spontaneous at all
temperatures.
∆Gorxn = ∆Horxn - T∆Sorxn
Reaction 2:
Since ∆Ho and ∆So have similar sign, therefore reaction 2 becomes less
spontaneous as temperature increases (∆Gorxn going to be positive at
higher temperature) and becomes more spontaneous as temperature
decreases ( for ∆Gorxn = negative).

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Q10

Define path function and give two examples of quantities that are path
function.
• JAN 2018

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Answer Q10

Path function is a function that depends on the path of the process.

Examples:

Heat, q = mc∆T
Work, w = F x d

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Q11
A certain gas expands in volume from 2.0L to 6.0L at constant
temperature. During this process, there is a heat transfer of 128J from
the gas to the surroundings.

i) Calculate the work (in Joule) by the gas if it expands against a

constant pressure of 1.2atm.
ii) Calculate the internal energy change for this process.
• JAN 2018

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Answer Q11

i) W = - P∆V
= - (1.2 atm)(6.0L - 2.0L)
= - 4.8 L. atm or 4.8 [Link] x 101.3 J/ 1 [Link] = -486.24 J

ii) ∆E = q + w
= (- 128 J) + (- 486.24 J)
= - 614.24 J

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Q12

Discuss briefly how the entropy would change when sodium chloride is
cooled from 25oC to 0oC.
• JAN 2018

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Answer Q12

When temperature is reduced, the randomness of particles or entropy

of sodium chloride will be decreased.

Thus, the entropy change becomes zero (particles of sodium chloride

do not move at all at 0oC).

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Q13
For the decomposition of O3(g) to O2(g) as shown in equation below.

2O3(g) → 3O2(g)

Given ∆Ho = -285.4 kJ mol-1 and ∆So = 137.55 J K-1 mol-1 at 298K.

i) Determine ∆Go for the reaction.

ii) Predict either the reaction is more or less favorable as the
temperature increases.
• JAN 2018
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Answer Q13
i) ∆Gorxn = ∆Horxn - T∆Sorxn
= (-285.4 kJ mol-1) - (298 K)(137.55 J K-1 mol-1 / 1000)
= - 326.4 kJ mol-1

ii) As the temperature increases, the reaction is more favorable due

to the value of ∆Go becomes more negative (the reaction is always
spontaneous at low and high temperature).

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Q14
The equilibrium constant, Kp for the following reaction is 4.40 at 2000K.

H2(g) + CO2(g) ↔ H2O(g) + CO(g)

Calculate ∆G for the reaction and predict the direction toward

equilibrium when the partial pressures are PH2 = 0.25atm, PCO2 =
0.78atm, PH2O = 0.66atm and PCO = 1.20atm.
• JAN 2018

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Answer Q14
∆G = ∆Go + RT ln Q , At equilibrium, ∆G = 0 , Q = K
∆Go = - RT ln K
When K = 4.40 at T = 2000 K
∆Go = - (8.314 J K-1 mol-1)(2000 K) ln 4.40
= - (16628 J mol-1)(1.48)
= - 24609.44 J mol-1 @ - 24.6 kJ mol-1

H2(g) + CO2(g) ↔ H2O(g) + CO(g)

If partial pressures are PH2 = 0.25atm, PCO2 = 0.78atm, PH2O = 0.66atm and PCO = 1.20atm,
Q = (PH2O )(PCO ) = (0.66)(1.20) = 4.06
(PH2 )(PCO2 ) (0.25)(0.78)

∆G = ∆Go + RT ln Q
= - 24609.44 + (8.314)(2000) ln 4.06 = - 1.33 kJ mol-1

The reaction is shifted to the right to achieve equilibrium (forward reaction – spontaneous)
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Q15
Predict the sign of ∆S and give the reason for each of the following:

i) C(s) + H2O(g) ⇾ CO(g) + H2(g)

ii) N2(g) + 3H2(g) ⇾ 2NH3(g)
iii) C (s, graphite) ⇾ C(s, diamond)
• JUN 2018

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Answer Q15
i) C(s) + H2O(g) ⇾ CO(g) + H2(g)
∆S = +ve (increase in the number of gas molecules)

ii) N2(g) + 3H2(g) ⇾ 2NH3(g)

∆S = -ve (decrease in the number of gas molecules)

iii) C (s, graphite) ⇾ C(s, diamond)

∆S = -ve
(Diamond is harder solid than graphite, thus more restricted atom
motion in the crystal as compared to graphite)

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Q16
Ethanol is a renewable fuel made from plant materials.

i) Write an equation for the enthalpy of formation for ethanol, C2H5OH (l).
ii) By using the values in Table 1, calculate ∆H for the formation of C2H5OH (l) at
standard condition.

Table 1
Substance Sof (J/[Link]) ∆Gof (kJ /mol)
C (s, graphite) 5.74 0
H2(g) 130.57 0
O2(g) 205.03 0
C2H5OH (l) 282.6 -168.57
• JUN 2018

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Answer Q16
i) The equation for the enthalpy of formation for ethanol, C2H5OH (l).
2C (s) + 3H2(g) + ½ O2 (g) → C2H5OH (l)

ii) ∆Gof C2H5OH = [∑ ∆Gof products] – [∑∆Gof reactants]

= (- 168.57 kJ mol-1 ) - 0
= - 168.57 kJ mol-1

∆Sof C2H5OH = [∑ ∆Sof products] – [∑∆Sof reactants]

= (282.6 J K-1 mol-1 ) - [2(5.74) + 3(130.57) + ½ (205.03) J K-1 mol-1 ]
= - 223.11 J K-1 mol-1 @ - 0.22311 kJ K-1 mol-1

∆Go = ∆Ho - T∆So

∆Ho = ∆Go + T∆So
= (- 168.57 kJ mol-1 ) + (298 K) (0.22311 kJ K-1 mol-1 )
= - 102.1 kJ mol-1
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Q17

Show that the enthalpy change for a process with P-V work is equal to
the heat added at constant pressure (ie: ∆H = qp).

• JUN 2018

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Answer Q17
At constant pressure; enthalpy change is:

∆H = ∆E + P∆V

∆E = q + w (w = -P∆V) - work done by the system

∆E = q + (-P∆V)
Rearrange ; q = ∆E + P∆V

Therefore, ∆H = qp (heat at constant pressure)

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Q18
At 25oC, the formation of phosphorus trichloride from the most stable
elements has a negative ∆Ssys.

P4(s) + 6Cl2(g) ⇾ 4PCl3(g) ∆Ssys = -131 J K-1 mol-1

i) Give one factor that affects the entropy (S) of a system.

ii) Given ∆Hof of PCl3 is -287 kJ mol-1. Calculate the ∆Suniv and ∆Ssurr for
the formation reaction.
• DEC 2018

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Answer Q18
i) Temperature, Phase change, Atomic Size, Dissolution or Molecular Complexity

ii) P4(s) + 6Cl2(g) ⇾ 4PCl3(g) ∆Ssys = -131 J K-1 mol-1

∆Hrxn = ∑∆Hof products - ∑∆Hof reactants

= [4 (∆Hof PCl3)] - [ 1(∆Hof P4) + 6(∆Hof Cl2)]
= [4(-287 kJ mol-1)] - (0 + 0)
= - 1148 kJ mol-1

∆S surr = - ∆Hrxn = - (- 1148 kJ mol-1 ) = 3.85 kJ K-1mol-1 = 3850 JK-1mol-1

T 298 K

∆Suniv = ∆Ssys + ∆Ssurr = -131 + (3850) = 3714.9 J K-1 mol-1

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Q19
Calculate ∆Sorxn for the following reaction at 25oC and state whether the
reaction occurs spontaneously at this temperature.

CH3OH(g) ⇾ CO(g) + 2H2(g)

Given ∆So of CH3OH(g), ∆So of CO(g) and ∆So of H2(g) are 238.0 J K-1mol-1,
197.5 J K-1 mol-1 and 130.6 J K-1mol-1, respectively.
• DEC 2018

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Answer Q19
CH3OH(g) ⇾ CO(g) + 2H2(g)

∆Sorxn = ∑ ∆So products - ∑∆So reactants

= [ 1∆So CO + 2∆So H2 ] - [ 1∆So CH3OH]

= [ 1(197.5) + 2(130.6) ] - [ 1(238.0)]

= 220.7 J K-1 mol-1

Since ∆Sorxn > 0, the reaction is spontaneous at 25oC.

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Q20

The equilibrium constant (Kc) for the reaction below is 9.1 x 10-6 at
25oC.

2Fe3+(aq) + Hg22+(aq) ↔ 2Fe2+(aq) + 2Hg2+(aq)

If the [Fe3+] = 0.20M, [Hg22+] = 0.01M, [Fe2+] = 0.01M and [Hg2+] =

0.025M, calculate both standard Gibbs free energy change (∆Go) and
Gibbs free energy change (∆G) for this reaction.
• DEC 2018

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Answer Q20
∆Go = - RT ln K
= - (8.314) (298) ln 9.1 x 10-6
= 28.76 J mol-1

2Fe3+(aq) + Hg22+(aq) ↔ 2Fe2+(aq) + 2Hg2+(aq)

Q = [Fe2+ ]2[Hg2+ ]2 = (0.01)2 (0.025)2 = 1.56 x 10-4

[Fe3+ ]2[Hg22+] (0.20)2 (0.01)

∆G = ∆Go + RT ln Q
= 28.76 + (8.314) (298) ln 1.56 x 10-4
= 21.69 J mol-1
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Q21

State the Third Law of Thermodynamics.

• JUN 2019

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Answer Q21

The third law of thermodynamics states that it is impossible to attain

absolute zero temperature.
The entropy of pure crystalline substance at absolute zero (0 Kelvin) is
zero; S(0K)= 0.
The condition of S = 0 corresponds to perfect order.

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 Q22
A reaction that occurs in the internal combustion of engine is shown in the following equation:
N2(g) + O2(g) → 2NO(g)

Use the data in Table 1:

Table 1: Thermodynamic data for selected elements and compounds at 25oC
Substance ∆Hof (kJ mol-1) So (J K-1 mol-1)
NO(g) 90.29 210.65
O2(g) 0 205.0
N2(g) 0 191.5

i) Calculate the standard of enthalpy change, ∆Ho and entropy change, ∆So for the reaction at 298K.
ii) Find the standard Free Gibbs energy change, ∆G at 100oC and 3540oC.
iii) Discuss the significance of different values of ∆Go.
• JUN 2019

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Answer Q22
N2(g) + O2(g) → 2NO(g)

i) ∆Horxn = ∑ 2 ∆Hof NO - ∑ (∆Hof N2 + ∆Hof O2)

= 2 (90. 29) - (0 + 0)
= 180.58 kJ mol-1

∆So = ∑ 2 ∆So NO - ∑ (∆So N2 + ∆So O2)

= 2 (210.65) - (191.5 + 205.0)
= 421.30 - 396.5
= 24.80 J K-1 mol-1 @ 0.0248 kJ mol-1

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Answer Q22 (cont’d)
ii) At 100oC,
∆G = ∆H - T∆S
= (180.58 kJ mol-1) - (273 + 100 K) (0.0248 kJ K-1 mol-1)
= + 171.33 kJ mol-1

At 3540oC,
∆G = ∆H - T∆S
= (180.58 kJ mol-1) - (273 + 3540 K) (0.0248 kJ K-1 mol-1)
= + 86.02 kJ mol-1

The value of ∆G became smaller at higher temperatures. The reaction is not

spontaneous at any of these temperatures; however, the reaction becomes less
nonspontaneous as the temperature increases.
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Q23

Discuss how enthalpy change, ∆H and entropy change, ∆S will affect

∆G, and how the ∆G can be used as a criterion for spontaneity.

• JUN 2019

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Answer Q23

∆H ∆S ∆G Spontaneity
-ve +ve -ve Spontaneous at all temperatures
+ve -ve +ve Non-spontaneous at all temperatures
-ve -ve -ve or +ve Spontaneous toward low temperature
Non-spontaneous toward high temperature
+ve +ve -ve or +ve Spontaneous toward high temperature
Non-spontaneous toward low temperature

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Q24

Define enthalpy in terms of internal energy, pressure and volume.

• DEC 2019

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Answer Q24

Enthalpy (∆H) is the sum of the internal energy (∆E) of the system plus
the product of the pressure (P) of the gas in the system and its volume
(V).
∆H = ∆E - P∆V

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Q25

A system gives off 205 J of heat to surroundings and undergoes

compression at the same time with 68 J of work done on it. Calculate
the value of internal energy changes for this process.

• DEC 2019

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Answer Q25

q = - 205 J (heat is released to surroundings)

w = + 68 J (work done on the system)

∆E = q + w
= (-205 J) + (+68 J)
= - 137 J

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Q26

State the entropy changes for the following processes:

i) Sodium choride, NaCl(s) dissolves in water.

ii) Oxygen gas, O2(g) dissolves in water.
• DEC 2019

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Answer Q26
i) Dissolution of NaCl(s) in water.
Entropy increases (more disorder or more random)

ii) Dissolution of O2 (g) in water.

Entropy decreases (less disorder or less random).

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Q27
Methanol is produced by the following catalytic reaction at 25oC. The
enthalpy (∆Ho) and entropy (∆So) changes for the reaction are -128.1 kJ
mol-1 and -332.3 J K-1 mol-1, respectively.

CO(g) + 2H2(g) → CH3OH(l)

i) Show that the reaction is thermodynamically feasible at 25oC.

ii) Determine the spontaneity of the reaction at 500oC.
iii)Briefly discuss the spontaneity of the reactions at 25oC and 500oC.
• DEC 2019

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Answer Q27
i) ∆Go = ∆Ho - T∆So
= (-128.1 kJ mol-1) - (273 + 25 K) (-0.3323 kJ K-1 mol-1)
= - 29.07 kJ mol-1

ii) ∆Go = ∆Ho - T∆So

= (-128.1 kJ mol-1) - (273 + 500 K) (-0.3323 kJ K-1 mol-1)
= + 128.8 kJ mol-1

iii) Both sign of ∆Ho and ∆So are negative, spontaneity of the reaction
depends on the temperature. The reaction is more spontaneous at lower
temperature and becomes less spontaneous at higher temperature.

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