01-10-2024

CHEMISTRY
19th class Date : 30-09-2024

Dr Dr. K. Ananthanarayanan
Associate Professor (Research)
Department of Chemistry
Room No 319, 3rd Floor, Sir. C.V. Raman Research Park

Email : ananthak@srmist.edu.in
Phone : 9840154665
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CALCULATION OF ENTROPY

The standard entropy (ΔSᵒ) of a substance is the value of entropy

of the substance at 298 K and 1 atm.
CH4(g) + 2 O2 (g) → CO2 (g) + 2 H2O (l)
From the Table of Thermodynamic Data, the Standard entropies of
the substances involved in the above reaction are:
substances ΔS (J/K.mol)
CH4(g) 186
O2(g) 205
CO2(g) 214
H2O(l) 70

 The entropy change of the reaction can be calculated as:

 ΔSᵒreaction = ΣnpS(products) - ΣnrS(reactants)
 ΔSᵒ = [214 + 70 * 2] - [186 + 205 * 2] = -242 J/K
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Of the following reactions, which of the following is only

spontaneous at high enough temperatures?

∆H +, ∆S +
∆H +, ∆S –
∆H –, ∆S –
∆H –, ∆S +

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Given, ∆H = -120 kJ, ∆S = -150 JK -1

Remember to divide ΔS by 1000 J/kJ so that after you

multiply by temperature, T , it will have the same units, kJ , as
ΔH .

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ΔG = ΔH – TΔS

Given, ∆H = -120 kJ, ∆S = -0.15 kJ/K

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Is the following reaction spontaneous ? If so at what

temperature ?

Given ∆G°= -53.2 kJ, ∆H°= -21.5 kJ, and ∆S°=14.7J/K?

2NO (g) + O2 (g) → (2NO)2 (g)

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For a process to occur spontaneously:

a) the entropy of the system must increase

b) the entropy of the surroundings must increase
c) both the entropy of the system and the entropy of the
surroundings must increase
d) the net change in entropy of the system and surroundings
considered together must be a positive quantity
e) the entropy of the universe must remain constant

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Problems

A sample of gas expands in volume from 2.0 L to 6.0 L at constant

temperature. Calculate the work (in joules) done by the gas if it expands (a)
against a vacuum and (b) against a constant external pressure of 1.2 bar.

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Solution – Problem 1

A) Because the total number of molecules decreases in this reaction,

the system becomes more ordered. The entropy of the system
therefore decreases.
(b) Gases are more disordered than the corresponding liquids, so the
entropy of the system increases.
(c) Reactions in which a compound decomposes into two products
lead to an increase in entropy because the system becomes more
disordered. The increase in entropy in this reaction is even larger
because the starting material is a solid and one of the products is a
gas.
(d) The NH4+ and NO3- ions are free to move in a random fashion
through the aqueous solution, whereas these ions are locked into
position in the crystal. As a result, the entropy of the system
increases in this reaction.

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Problem 2

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Problem - 3

Using standard thermodynamic values, calculate the enthalpy of

the reaction of the combustion of butane gas with oxygen
gas to form carbon dioxide and liquid water.

ΔHf H2O(l) = -285.83 kJ/mol

ΔHf CO2(g) = -393.51 kJ/mol

ΔHf C4H10(g) = -61.87 kJ/mol

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Solution – Problem 3

 Chemical Equation:

2C4H10(g) + 13 O2(g) => 8 CO2(g) + 10 H2O(l)

ΔHrxn = [8*(-285.83 kJ) + 10 (-393.51 kJ)] – [(13*0 kJ)

+ 2(-61.87 kJ)] =

- 6093.41 kJ/mol

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Problem – 4

 Determine ΔStotal and decide whether the following

reaction is spontaneous at 298K. Given ΔH° = -24.8 kJ,
ΔS° = 15 J K-1

 The heat evolved in the reaction is 24.8 kJ. The same

quantity of heat is absorbed by the surroundings.
 Hence, Entropy change of the surrounding will be,
 ΔSsurr = -ΔHsystem° / T
 = – [(-24.8 (kJ)) / 298 (K)]
 + 83.2 J K-1

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 ΔStotal = ΔSSystem + ΔSSurr

 ΔSSys = ΔS° = 15 J K-1
 = 15(J K-1) + 83.2 (J K-1)
 = 98.2 J K-1
 As ΔStotal is positive, the reaction is spontaneous at 298
K.

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Problem – 5

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Problem – 6

 Calculate Kp for the reaction at 513 K,

2NOCl (g) ⟶ 2NO(g) + Cl2(g) with ΔG° = 17.38 kJ mol-1.

 ΔG° = -2.303 RT log10 Kp, ΔG° = 17.38 kJ mol-1, R = 8.314 J

K-1 mol-1, T = 513K

 Hence,
 log10 kp = – ΔG° / 2.303 RT
 = – (17380(J mol-1) / 2.303 × 8.314 ( J K-1 mol-1) ×
513(K))
 = -1.769
 Hence, Kp = antilog(-1.769)
 = 0.017
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Problem 7

 Using standard thermodynamic data, calculate the

equilibrium constant at 298.15 K for the reaction shown
below. Predict whether this reaction is feasible at this
temperature and what does K value tells about the reaction?

Fe(s) + 2 HCl(aq) → FeCl2(s) + H2(g)

ΔG0f (FeCl2) = -302.3 kJ/mol

ΔG0f (HCl) = -131.2 kJ/mol

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Solution – Problem 7
Fe(s) + 2 HCl(aq) → FeCl2(s) + H2(g)

The large negative ∆Gº and K value tells us that the position
of equilibrium for this reaction lies very far toward products.

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Problem - 8

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Solution - 8

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This reaction is spontaneous at room temperature since ΔGo is

negative. Therefore NH4NO3(s) will dissolve in water at room
temperature.
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Problem - 9

Calculate H and S for the following reaction and decide in which

direction each of these factors will drive the reaction.
N2(g) + 3 H2(g) ⇌ 2 NH3(g)

Compound  Hfo(kJ/mol)  S(J/mol-K)

N2(g) 191.61
H2(g) 130.68
NH3(g) -46.11 192.45

Use the values of H and S calculated in this problem to predict

whether the following reaction is spontaneous at 25 deg C and/or at
500 deg C

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Solution – Problem 9

Ho = Hfo(products) - Hfo(reactants)

= [2 mol NH3 x 46.11 kJ/mol] - [1 mol N2 x 0 kJ/mol + 3 mol H2 x 0 kJ/mol]
= -92.22 kJ
The reaction is exothermic ( Hº < 0), which means that the enthalpy of
reaction favors the products of the reaction:

So = So(products) - So(reactants)

= [2 mol NH3 x 192.45 J/mol-K] - [1 mol N2 x 191.61 J/mol-K + 3 mol
H2 x 130.68 J/mol-K]
= -198.75 J/K

The entropy of reaction is unfavorable, however, because there is a

significant increase in the order of the system, when N2 and H2 combine to
form NH3.

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Before we can decide whether the reaction is still spontaneous we need to

calculate the temperature of the kelvin scale:
TK = 500o C + 273 = 773 K
We then multiply the entropy term by this temperature and subtract this
quantity from the enthalpy term:
Go773 = Ho298 - T So298
= 92,220 J - (773 K x -198.75 J/K)
= 92,220 J - (-153,600 J)
= 61,380 J
Go = 61.4 kJ
Because the entropy term becomes larger as the temperature increases,
the reaction changes from one which is favorable at low temperatures
to one that is unfavorable at high temperatures.

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Recap, functions and terms

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Recap, functions and terms

ΔG = ΔH – TΔS

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Gibbs – Helmholtz equation

 The Gibbs–Helmholtz equation is a thermodynamic equation

used for calculating changes in the Gibbs energy of a
system as a function of temperature, where H is the
enthalpy, T the absolute temperature and G the Gibbs free
energy of the system, all at constant pressure p.
 The equation states that the change in the G/T ratio at
constant pressure as a result of an infinitesimally small
change in temperature is a factor H/T2.

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 The equation states that the change in the G/T ratio at

constant pressure as a result of an infinitesimally small
change in temperature is a factor H/T2.

 The main difference between Gibbs and Helmholtz free

energy is that Gibbs free energy is defined under constant
pressure, while Helmholtz free energy is defined under
constant volume.

 The Gibbs free energy is often used since it considers a

constant pressure condition.

 The Helmholtz free energy is not much used because it

considers a constant volume condition.
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This reaction is spontaneous since ΔG is negative.

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Chemical Equilibrium

 A state in which both the reactants and products are present in

concentrations which have no further tendency to change with
time, so that there is no observable change in the properties of
the system.
 Results when the forward reaction proceeds at the same rate
as the reverse reaction.
 The reaction rates of the forward and backward reactions are
generally not zero, but they are equal.
 Thus, there are no net changes in the concentrations of the
reactants and products.
 Such a state is known as dynamic equilibrium

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Chemical Equilibrium
Le Châtelier’s Principle

What Happens When a System at Equilibrium is Perturbed?

 Change concentration, temperature, pressure or add other chemicals

Equilibrium is re-established
Reaction accommodates the change in products, reactants, temperature, pressure, etc.
Rates of forward and reverse reactions re-equilibrate.

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Chemical Equilibrium
Le Châtelier’s Principle, Effect of Temperature on Equilibrium

Combine Gibbs free energy and Equilibrium Equations:

Only Enthalpy term is temperature dependent:

A graph of lnK (y-axis) vs. 1/T (x-axis) has a slope related to the standard
enthalpy change and a y-intercept related to the standard entropy change for
the equilibrium. Once the values of ∆Hº and ∆Sº are both known, it is a relatively
trivial process to find ∆Gº using the following expression.

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Chemical Equilibrium
Le Châtelier’s Principle

Effect of Temperature on Equilibrium

Combine Gibbs free energy and Equilibrium Equations:

 G  H o  TS 
o

K e RT e RT

e

 H
o

RT
 S
R

 H o S o
e RT e R

Only Enthalpy term is temperature dependent:

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 For an endothermic reaction, ΔH > 0 (and the gas constant R >

0), so slope is less than 0. Thus, for an endothermic reaction, the
van't Hoff plot should always have a negative slope.

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 For an exothermic reaction, ΔH < 0 . Thus, for an exothermic

reaction, the van't Hoff plot should always have a positive slope.

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Thank you all for your

attention

Information presented here were collected from various sources –

textbooks, articles, manuscripts, internet and newsletters. All the
researchers and authors of the above mentioned sources are greatly
acknowledged.

121CYB101J-Chemistry
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