Chemical Engineering Thermodynamics (CHE181403)

REVERSIBLE AND IRREVERSIBLE PROCESSES

Processes occur when there exists a driving force for a change of state between the parts of the system or between the
system and the surroundings. If this driving force is finite, the process is irreversible and if it is infinitesimal in magnitude,
the process is reversible.
All spontaneous processes occurring in nature are irreversible. They cannot be reversed without the use of external energy.
If the system undergoing an irreversible process were to be brought back to its initial state, the surroundings would have
to undergo some change through heat or work interactions. In short, as a result of the processes in the forward and reverse
directions, if changes remain in the surroundings or in the system itself, the process would be irreversible. E.g., The free
expansion of a gas is a highly irreversible process.
In contrast, the direction of a reversible process can be changed by an infinitesimal change in the forces acting on the
system. A system undergoing a reversible process can be brought back to its original state, leaving no change in the
surroundings.
Example 7. A stationary mass of gas is compressed without friction from an initial state of 0.3 m3 and 0.105 MPa to a final
state of 0.15 m3 and 0.105 MPa, the pressure remaining constant during the process. There is a transfer of 3 7 .6 kJ of heat
from the gas during the process. How much does the internal energy of the gas change? (-21.85 kJ)
Example 8. When a system is taken from state a to state b, in Fig., along path acb, 84 kJ of beat flow into the system, and
the system does 32 kJ of w'ork. (a) How much will the heat that flows into the system. along path a db, if the work done is
10.5 k.J? (b) When the system is returned from b to a along the curved path, the work done on the system is 21 kJ. Does
the system absorb or liberate heat, and how much of the heat is absorbed or liberated? (c) If Ua = 0 and Ud = 42 kJ, find the
heat absorbed in the processes ad and db.

(a) 62.5 kJ, (b) -73kJ, (c) 52.5 kJ, 10kJ (db path)
Show that CP – CV = R for an ideal gas.
Proof: 𝐻 = 𝑈 + 𝑃𝑉
𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑃𝑉)
𝑑𝐻 = 𝑑𝑈 + 𝑑(𝑅𝑇) [𝑓𝑜𝑟 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠 𝑃𝑉 = 𝑅𝑇]
= 𝑑𝑈 + 𝑅 𝑑𝑇
𝐶𝑝 𝑑𝑇 = 𝐶𝑉 𝑑𝑇 + 𝑅𝑑𝑇

𝐶𝑝 − 𝐶𝑉 = 𝑅

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

Module 2
Heat capacities of gases as a function of temperature
We know, ∆𝐸 = ∫ 𝐶𝑣 𝑑𝑇 𝑎𝑛𝑑 ∆𝐻 = ∫ 𝐶𝑝 𝑑𝑇

In these equations when Cp and Cv are constants then ΔE and ΔH can be easily calculated. Cp and Cv can be considered
to be constant when the temperature change is very small. However, when large temperature changes are considered, in
general these expressions can be integrated only when heat capacity is known as a function of temperature.
For an ideal gas i.e., at zero pressure, Cp and Cv are related by: Cp – Cv = R (zero pressure)
However, they are approximately valid for pressures up to several atmospheres and are sufficiently accurate for almost all
calculations involving gases at atmospheric pressure.
The heat capacities of gases in the zero pressure state increases smoothly as temperature increases. The analytical
relationship most frequently used to relate point values of Cp with temperature has the form:
𝐶𝑝 = 𝛼 + 𝛽𝑇 + 𝛾𝑇 2 … … … … … … . (1)

𝛼, 𝛽, 𝑎𝑛𝑑 𝛾 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠

𝑇 𝛽 𝛾
Therefore, ∆𝐻 = ∫𝑇 2 𝐶𝑝 𝑑𝑇 = 𝛼(𝑇2 − 𝑇1 ) + 2 (𝑇22 − 𝑇12 ) + 3 (𝑇23 − 𝑇13 ) … … … … … … . (2)
1

Concept of mean heat capacity (𝑪𝒑𝒎𝒆𝒂𝒏 )

Since ∫ 𝐶𝑝 𝑑𝑇 must be evaluated frequently, a short cut method for doing so has been developed in terms of‘ mean heat
capacity(𝑪𝒑𝒎𝒆𝒂𝒏 ) and is often used for most common gases.
𝑇
The mean heat capacity is defined as ∫𝑇 2 𝐶𝑝 𝑑𝑇 = 𝑪𝒑𝒎𝒆𝒂𝒏 (𝑇2 − 𝑇1 )
1

𝛽 𝛾
Where, 𝑪𝒑𝒎𝒆𝒂𝒏 = 𝛼 + 2 (𝑇2 + 𝑇1 ) + 3 (𝑇12 + 𝑇1 𝑇2 + 𝑇22 )

Heat Effects Accompanying Phase Change

When a pure substance is liquefied from the solid state or vaporized from the liquid state at constant pressure, there is no
change in temp, but there is a definite transfer of heat from the surrounding to the system. These effects are called “Latent
heat of fusion” and “Latent heat of vaporization” respectively.
The characteristic features of all such processes is the co-existence of two phases, so that the state is determined by the
specification of one intensive property. Under such condition, there is a fundamental relationship between the latent heat
accompanying the transfer of material between the two phases and P-V-T data for the system. This is called CLAUSIUS-
CLAPEYRON EQUATION given by
𝑑𝑃 𝜆
=
𝑑𝑇 𝑇Δ𝑉
𝑑𝑃
𝑖𝑠 𝑡ℎ𝑒 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑣𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑤𝑖𝑡ℎ 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒
𝑑𝑇
𝜆 𝑖𝑠 𝑡ℎ𝑒 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡
Δ𝑉 𝑖𝑠 𝑡ℎ𝑒 𝑣𝑜𝑙𝑢𝑚𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑎𝑐𝑐𝑜𝑚𝑝𝑎𝑛𝑦𝑖𝑛𝑔 𝑡𝑜 𝑡ℎ𝑒 𝑝ℎ𝑎𝑠𝑒 𝑐ℎ𝑛𝑎𝑔𝑒 𝑎𝑡 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇
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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

To obtain the integrated form of CLAUSIUS-CLAPEYRON EQUATION from the exact CLAPEYRON equation some
assumptions are made as –
1. The volume of the liquid phase is negligible compared to that of the vapor phase.
2. The vapor phase behaves as an ideal gas.
3. The heat of vaporization is independent of temperature.
𝑑𝑃 𝜆
=
𝑑𝑇 𝑇Δ𝑉
𝑑𝑃 𝜆
=
𝑑𝑇 𝑇(𝑉𝑔 − 𝑉𝑙 )

𝑑𝑃 𝜆
= (𝑎𝑠𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 1)
𝑑𝑇 𝑇𝑉𝑔

𝑑𝑃 𝑃𝜆
= [𝑎𝑠𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 (2), 𝑃𝑉𝑔 = 𝑅𝑇]
𝑑𝑇 𝑅𝑇 2

𝑃2
𝑑𝑃 𝜆 𝑇2 𝑑𝑇
∫ = ∫ (𝑎𝑠𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 3)
𝑃1 𝑃 𝑅 𝑇1 𝑇 2

𝑃2 𝜆 1 1
ln =− ( − )
𝑃1 𝑅 𝑇2 𝑇1
This Eq. is known as Clausius - Clapeyron Eq.
Example 1. Calculate the vapor pressure of water at 363 K, if the vapor pressure at 373 K is 101.3 kPa. The mean heat of
vaporization in this temperature range is 2275 kJ/kg.
Solution:
𝑃2 𝜆 1 1
ln =− ( − )
𝑃1 𝑅 𝑇2 𝑇1
𝑃2 2275 1 1
ln =− ( − ) = −0.37
101.3 0.462 363 373
𝑃2 = 70 𝑘𝑃𝑎
The Standard Heat of Reaction
The standard heat of reaction at a temperature T is the enthalpy change accompanying a reaction when both the reactants
and products are at their standard states at temperature T. It is represented by the symbol Δ𝐻𝑇0 , the superscript ‘0’ indicates
that the heat of reaction refers to the standard conditions. By convention, the standard heats of reaction are reported at a
0
temperature of 298 K and are represented by Δ𝐻298

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Sanjay Paul

0
2𝐶(𝑠) + 𝑂2 (𝑔𝑎𝑠) → 2𝐶𝑂(𝑔𝑎𝑠); Δ𝐻298 = −221.2 𝑘𝐽

𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = ∑ 𝐻 − ∑ 𝐻

𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

positive values of ΔH indicate increase in the enthalpy and therefore represent endothermic reactions.
negative values of ΔH mean decrease in enthalpy and so exothermic reactions.
The Standard Heat of Combustion
When the reaction under consideration is a combustion reaction, the heat of reaction is known as heat of combustion. Or,
the ‘heat of combustion of a substance’ is the heat of reaction when a substance is oxidized with molecular oxygen.
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𝐶𝐻3 𝐶𝐻𝑂(𝑙) + 𝑂2 (𝑔) → 2𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙); ∆𝐻𝐶0 = −1168.12 𝑘𝐽
2
When water formed during combustion is in the liquid state, the energy liberated will be more than the energy liberated
when the combustion products contain water in the vapor-state. The heating value in the former case is known as gross
heating value, and that in the latter is known as net heating value.
The Standard Heat of Formation
The change in enthalpy accompanying the formation of 1 mole of a substance from the constituent elements is termed the
heat of formation. When the reactants and products are at their standard states, the heat of formation is called standard heat
of formation.
3 1
𝐶(𝑠) + 𝐻2 (𝑔) + 𝐶𝑙2 (𝑔) → 𝐶𝐻3 𝐶𝑙(𝑔); ∆𝐻𝑓0 = −82𝑘𝐽
2 2
Hess’s Law of Constant Heat Summation
Heat of reaction represents the difference between enthalpy of products and enthalpy of reactants. Enthalpy, as we know,
is a state function and the heat of reaction, therefore, depends only on the initial and final states, no matter how the change
from this initial to the final state is achieved. The net heat evolved or absorbed in a chemical reaction is the same whether
the reaction takes place in a single step or in a series of steps. This is known as Hess’s law.
Example 2. Calculate the heat of formation of methane gas from the following heat of combustion data:
0
(a) 𝐶𝐻4 (𝑔) + 2𝑂2 (𝑔) → 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙); ∆𝐻298 = −890.94 𝑘𝐽
0
(b) 𝐶(𝑠) + 𝑂2 (𝑔) → 𝐶𝑂2 (𝑔); ∆𝐻298 = −393.78 𝑘𝐽
1 0
(c) 𝐻2 (𝑔) + 2 𝑂2 (𝑔) → 𝐻2 𝑂(𝑙); ∆𝐻298 = −286.03 𝑘𝐽

Solution: consider the operation: 2 x Eq. (c) + Eq. (b) – Eq. (a). this gives
𝐶(𝑠) + 2𝐻2 (𝑔) → 𝐶𝐻4 (𝑔); ∆𝐻𝑓0 = −(2 × 286.03) − 393.78 + 890.94 = −74.9 𝑘𝐽

Effect of Temperature on Standard Heat of Reaction

How would you determine the standard heat of reaction at temperature T if the standard heat of reaction is given at
temperature T1?

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

The actual reaction occurring at temperature T, for which the standard heat of reaction is ∆𝐻𝑓0 , may be treated as occurring
in three steps as depicted in Fig.

The reactants are cooled from temperature T to T1. The enthalpy change for this step is

The standard heat of reaction at temperature T, is obtained by adding the preceding three equations.

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

Example 3. The heat of reaction at 300 K and one atmosphere pressure for the following gas phase reaction: 𝐴 + 3𝐵 → 𝐶.
is –200 kJ per mol of A converted. Data on the molar heat capacity at constant pressure in (kJ/mol K) for the various
components are: 𝐶𝑝 𝑓𝑜𝑟 𝐴 = −1.7 × 10−3 + 3.4 × 10−4 𝑇, 𝑤ℎ𝑒𝑟𝑒 𝑇 𝑖𝑠 𝑖𝑛 𝐾, 𝐶𝑝 𝑓𝑜𝑟 𝐵 = 0.03 𝑎𝑛𝑑 𝐶𝑝 𝑓𝑜𝑟 𝐶 = 0.1
Calculate the heat of reaction at 500 K and at a pressure of 100 kPa.
Solution:

From Eq. (1)

Example 4. Calculate the standard heat of combustion of CH4 at 260°C. The products of combustion are CO2(g) and
H2O(g). The heat of combustion of CH4 at 25°C with liq.water as a product is -212,800 cal/gmole. Latent heat of water at
25 °C is10,520 cal/gmole. The average molal heat capacities from 298 to 533 K are:
CH4=10.0; O2=7.3; CO2=9.9; H2O=8.2

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

Thermodynamic Equilibrium
A system is said to exist in a state of thermodynamic equilibrium when no change in any macroscopic property is registered,
if the system is isolated from its surroundings. Thermodynamics studies mainly the properties of physical systems that are
found in equilibrium states.
A system will be in a state of thermodynamic equilibrium, if the conditions for the following three types of equilibrium are
satisfied:
(a) Mechanical equilibrium (ΔP=0) (b) Chemical equilibrium (Δµ=0) and (c) Thermal equilibrium (ΔT=0)
Quasi-Static Process: is a thermodynamic process that happens slowly enough for the system to remain in thermodynamic
equilibrium.
PROCESSES INVOLVING IDEAL GASES
1. Constant Volume Process (Isochoric Process ΔV=0) 𝑑𝑄 − 𝑑𝑊 = 𝑑𝑈
Work: Consider one mole of an ideal gas undergoing a constant volume process. Since the volume remains
constant, there is no work of expansion and dW = 0

Heat and Internal Energy: 𝑑𝑄 = 𝑑𝑈 = 𝐶𝑉 𝑑𝑇

𝑇1 𝑇2
P – V – T relation: =
𝑃1 𝑃2
2. Constant Pressure Process (Isobaric Process ΔP=0)
The heat supplied is the product of heat capacity and rise in temperature: dQ = CP dT
The work involved is given by: 𝑑𝑊 = 𝑃 𝑑𝑉
Change in internal energy: 𝑑𝑈 = 𝐶𝑉 𝑑𝑇
𝑇1 𝑇2
P – V – T relation: =
𝑉1 𝑉2
3. Constant Temperature Process (Isothermal ΔT=0)
Internal energy of an ideal gas will change only if the temperature changes. In an isothermal process involving an
ideal gas, the change in internal energy and the change in enthalpy would be zero.

We know, 𝑑𝑄 − 𝑑𝑊 = 𝑑𝑈
Putting, 𝑑𝑈 = 0 𝑑𝑄 = 𝑑𝑊
The above equation can be integrated to determine the heat and work effects in an isothermal process involving
ideal gases. 𝑄 = 𝑊 = ∫ 𝑃 𝑑𝑉

𝑄 = 𝑊 = 𝑅𝑇 ln 𝑉2 /𝑉1
𝑃1 𝑉2
P – V – T relation: =
𝑃2 𝑉1
Or
𝑄 = 𝑊 = 𝑅𝑇 ln 𝑃1 /𝑃2
4. Adiabatic Process (Q=0)
In an adiabatic process, there is no heat interaction between the system and the surroundings. dQ = 0
For an adiabatic process the pressure and volume are related as 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

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Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

𝐶𝑃
𝑤ℎ𝑒𝑟𝑒, 𝛾 = 𝑤ℎ𝑖𝑐ℎ 𝑖𝑠 𝑎𝑠𝑠𝑢𝑚𝑒𝑑 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑓𝑜𝑟 𝑎𝑛 𝑖𝑑𝑒𝑎𝑙 𝑔𝑎𝑠
𝐶𝑉
Putting dQ = 0 in first law, −𝑑𝑊 = 𝑑𝑈 = 𝐶𝑉 𝑑𝑇

or, −𝑑𝑊 = −𝑃 𝑑𝑉 = 𝐶𝑉 𝑑𝑇
𝑅𝑇
or, − 𝑑𝑉 = 𝐶𝑉 𝑑𝑇
𝑉
𝑅 𝑑𝑉 𝑑𝑇
or, −𝐶 = … … … … (1)
𝑉 𝑉 𝑇

For an ideal gas, 𝐶𝑃 − 𝐶𝑉 = 𝑅

𝑅
or, 𝛾−1=𝐶
𝑉

Therefore, from Eq. (1)

𝑉2 𝑇2
𝑑𝑉 𝑑𝑇
−(𝛾 − 1) ∫ =∫
𝑉1 𝑉 𝑇1 𝑇

𝑇2 𝑉1
ln = (𝛾 − 1) ln
𝑇1 𝑉2

Change in internal energy, 𝑑𝑈 = 𝐶𝑉 (𝑇2 − 𝑇1 )

The work-done in the Adiabatic process, 𝑊 = 𝐶𝑉 (𝑇1 − 𝑇2 )

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𝑅𝑇1 −𝑅𝑇2 𝑃1 𝑉1 −𝑃2 𝑉2

or, 𝑊= =
𝛾−1 𝛾−1
5. Polytrophic Process
In a polytrophic process, the relationship between pressure and volume is assumed to be 𝑃𝑉 𝑛 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
where n is a constant. If n = 0, the process is isobaric; if n = 1, the process become isothermal; and if n = ∞, the
process is isochoric (constant volume). If n = γ, the process is an adiabatic process.
Generally, the value of n lies between 1 and γ, indicating that the process lies between isothermal and adiabatic.

EXAMPLE. An ideal gas is undergoing a series of three operations: The gas is heated at constant volume from 300 K and
1 bar to a pressure of 2 bar. It is expanded in a reversible adiabatic process to a pressure of 1 bar. It is cooled at constant
pressure of 1 bar to 300 K. Determine the heat and work effects for each step. Assume CP = 29.3 kJ/kmol K.
Solution:

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 Golaghat Engineering College
Chemical Engineering Thermodynamics (CHE181403)
Sanjay Paul

EXAMPLE Calculate the change in internal energy, change in enthalpy, work done, and the heat supplied in the following
processes:
(a) An ideal gas is expanded from 5 bar to 4 bar isothermally at 600 K.
(b) An ideal gas contained in a vessel of 0.1 m3 capacity is initially at 1 bar and 298 K. It is heated at constant volume to
400 K.
(Assume that CP = 30 J/mol K.)
Solution:

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