Chemical Engineering

Thermodynamics I

Heat Effects Accompanying Phase

Change

Lecturer: Engr. Dr. Babatunde D.E.

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Preamble
• Heat effects refer to physical and chemical phenomena that are
associated with heat transfer to or from a system or that result in
temperature changes within a system, or both.
• All chemical or biochemical process is associated with one or more
heat effects.
• When a fluid is heated (or cooled) by the purely physical direct
transfer of heat to (or from) the fluid, the temperature changes that
occur are known as sensible heat effects (it is referred to as sensible
heat effects because they may be detected by our sense perception
of temperature).
• Phase changes, physical processes occurring for a pure substance at
constant temperature and pressure, are accompanied by latent heats.
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• Chemical reactions are characterized by heats of reaction, which for
combustion reactions evolve heat.
• For flow processes designed for simple heating and cooling of gases,
liquids, and solids:

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 Heat Effects Accompanying Phase Change
• At constant pressure, pure substances can change phase without
temperature change occurring.
• However, such changes in phase are accompanied by heat transfer
(i.e the substance either absorbs heat or releases heat).
• When a substance is liquefied from the solid state, the heat effect is
called latent heat (or enthalpy) of fusion.
• When a substance is vaporized from the liquid, the heat effect is
called latent heat (or enthalpy) of vaporization.
• When a substance vaporizes from solid, the heat effect is called
latent heat (or enthalpy) of sublimation.
• Heats of transition also accompanies the change of one substance
from one allotropic solid state to another.
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• The processes of phase transition are all characterized by the
coexistence of two phases.
• According to the Gibb’s phase rule (𝐹 = 2 + 𝑁 − 𝑃), the intensive
state of a two-phase system consisting of a single species is
established by specifying just one intensive property.
• Thus the latent heat accompanying a phase change (from 𝛼 to 𝛽) is a
function of temperature only, and is related to other system
properties by an exact thermodynamic equation:
𝑠𝑎𝑡
𝑑𝑃
∆𝐻 𝛼𝛽 = 𝑇∆𝑉 𝛼𝛽 (1)
𝑑𝑇
Where for a pure species at temperature 𝑇,
∆𝐻 = 𝑙𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡
= 𝑒𝑛𝑡ℎ𝑎𝑙𝑝𝑦 𝑐ℎ𝑎𝑛𝑔𝑒 𝑎𝑐𝑐𝑜𝑚𝑝𝑎𝑛𝑦𝑖𝑛𝑔 𝑡ℎ𝑒 𝑝ℎ𝑎𝑠𝑒 𝑐ℎ𝑎𝑛𝑔𝑒
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∆𝑉 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑐ℎ𝑎𝑛𝑔𝑒 𝑎𝑐𝑐𝑜𝑚𝑝𝑎𝑛𝑦𝑖𝑛𝑔 𝑡ℎ𝑒 𝑝ℎ𝑎𝑠𝑒 𝑐ℎ𝑎𝑛𝑔𝑒
𝑃 𝑠𝑎𝑡 = 𝑠𝑎𝑡𝑢𝑟𝑎𝑡𝑖𝑜𝑛 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒,
• i.e., the pressure at which the phase change occurs, which is a
function of T only.
• Equation (1) is referred to as the Clapeyron equation.
• The Clapeyron equation predicts the dependence of equilibrium
pressure on temperature when two phases of a given substance
coexist.

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• When the Clapeyron equation is applied to the vaporization of a
pure liquid:
𝑑𝑃𝑠𝑎𝑡
• is the slope of the vapor pressure-versus-temperature curve at
𝑑𝑇
the temperature of interest.
• ∆𝑉 is the difference between molar volumes of saturated vapor and
saturated liquid.
• ∆𝐻 is the latent heat of vaporization.
• Hence, ∆𝐻 may be calculated from vapor-pressure and volumetric
data.
• Latent heats are also measured calorimetrically.

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• Clapeyron equation may be used for various purposes.
• It can be used to calculate the heat of vaporization, if the
variation of vapour pressure with temperature is known.
• Alternatively, if the heat of vaporization is available, it is possible
to predict the vapour pressure variation with temperature.
• The Clapeyron equation is also true for S – V equilibrium and S – L
equilibrium

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Worked example
The heat of fusion of ice to form water is 335 𝐽 𝑔. The densities of
water and ice are 1.00 𝑔 𝑐𝑚3 and 0.915 𝑔 𝑐𝑚3 . Calculate the
melting temperature of ice when the pressure is 110 𝑀𝑃𝑎.

Solution
∆𝐻 𝑓𝑢𝑠𝑖𝑜𝑛 = 335 𝐽 𝑔, 𝜌𝑙 = 1 𝑔 𝑐𝑚3 , 𝜌𝑠 = 0.915 𝑔 𝑐𝑚3
@ 𝑃 = 110 𝑀𝑃𝑎, 𝑇𝑠𝑙 =?
We know that at 0.101325 𝑀𝑃𝑎, ice melts at a temperature of 273 𝐾
Note: 1 𝑎𝑡𝑚 = 101,325 𝑃𝑎 = 101.325 𝑘𝑃𝑎 = 0.101325 𝑀𝑃𝑎;
0 ℃ = 273 𝐾
𝑉𝑙 = 1 𝑐𝑚3 𝑔, 𝑉𝑠 = 1 0.915 𝑐𝑚3 𝑔 = 1.0929 𝑐𝑚3 𝑔
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From equation (1),
∆𝐻 𝑓𝑢𝑠𝑖𝑜𝑛 𝑑𝑇 𝑠𝑎𝑡
= 𝑑𝑃
∆𝑉 𝑠𝑙 𝑇
𝑓𝑢𝑠𝑖𝑜𝑛
𝑠𝑎𝑡 𝑠𝑎𝑡
∆𝐻 𝑇2
𝑃2 − 𝑃1 = 𝑠𝑙
ln
∆𝑉 𝑇1
335 𝐽 𝑔 𝑇2
110 − 0.101325 𝑀𝑃𝑎 = 3
ln
1 − 1.0929 𝑐𝑚 𝑔 273
𝐽 𝑇2
109.899 𝑀𝑃𝑎 = −3,606.027 3 × ln
𝑐𝑚 273

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Note 1 𝐽 = 1 𝑃𝑎. 𝑚3 , 100 𝑐𝑚 = 1𝑚
109.899 𝑀𝑃𝑎
𝐽 1 𝑃𝑎. 𝑚3 100𝑐𝑚 3 𝑇2
= −3,606.027 × 1𝐽× × ln
𝑐𝑚3 1𝑚3 273
𝑇2
109.899 𝑀𝑃𝑎 = −3,606.027 𝑀𝑃𝑎 × ln
273
𝑇2
−0.03048 = ln
273
𝑇2 = 264.81 𝐾
When the pressure is 110 𝑀𝑃𝑎, ice will melt at 264.81 𝐾

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Derivation of the Clasius-Clapeyron equation
For the particularly important case of phase transition from liquid 𝑙 to
vapor 𝑣, the Clapeyron equation can be rewritten as follows:
𝑠𝑎𝑡
𝑑𝑃
∆𝐻 𝑙𝑣 = 𝑇∆𝑉 𝑙𝑣 (2)
𝑑𝑇
The change in molar volume in the Clapeyron equation can also be
expressed in terms of the gas law for the case of transition from liquid
to vapour:
𝑅𝑇 𝑅𝑇
∆𝑉 𝑙𝑣 = 𝑉𝑣 − 𝑉𝑙 = 𝑠𝑎𝑡 (𝑍 − 𝑍 ) = 𝑠𝑎𝑡 ∆𝑍 𝑙𝑣
𝑣 𝑙 (3)
𝑃 𝑃

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Combining equations (2) and (3),
𝑑𝑃 𝑠𝑎𝑡 ∆𝐻 𝑙𝑣
𝑠𝑎𝑡
= 2 𝑙𝑣
𝑑𝑇
𝑃 𝑅𝑇 ∆𝑍
𝑑 ln 𝑃 𝑠𝑎𝑡 ∆𝐻 𝑙𝑣
= (4)
𝑑𝑇 𝑅𝑇 2 ∆𝑍𝑙𝑣
𝑑 ln 𝑃 𝑠𝑎𝑡 ∆𝐻 𝑙𝑣
=− (5)
1 𝑅∆𝑍 𝑙𝑣
𝑑
𝑇
Equations (2), (4) and (5) are equivalent, exact forms of the Clapeyron
equation for vaporization of pure species.

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The Clapeyron equation for vaporization can be further simplified at
low pressure using the following approximations:
• At low pressure (temperature is not too near the critical point),
the molar volume of the liquid is negligible compared with the
molar volume of the vapor
• At low pressure, the vapor phase behaves like an ideal gas.
Hence, its compressibility factor is close to 1.

𝑠𝑎𝑡 𝑉 𝑣 𝑠𝑎𝑡 𝑉 𝑙
𝑃 𝑃
∆𝑍 𝑙𝑣 = 𝑍𝑣 − 𝑍𝑙 = − =1−0=1
𝑅𝑇 𝑅𝑇

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Then,

𝑑 ln 𝑃 𝑠𝑎𝑡
∆𝐻 𝑙𝑣 = −𝑅 (6)
1
𝑑
𝑇

Equation (6) is known as the Clausius-Clapeyron equation

The Clasius-Clapeyron equation indicates a direct proportionality to
𝑠𝑎𝑡 1
the slope of a plot of ln 𝑃 vs (vapour pressure curve)
𝑇

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Worked Example
Calculate the vapour pressure of water at 363 𝐾, if the vapour pressure
at 373 𝐾 is 101.3 𝑘𝑃𝑎 . The mean heat of vaporization in this
temperature range is 2275 𝑘𝐽/𝑘𝑔.
@ 𝑇 = 373 𝐾, 𝑃 = 101.3 𝑘𝑃𝑎
@ 𝑇 = 363 𝐾, 𝑃 =?
∆𝐻 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = 2275 𝑘𝐽 𝑘𝑔, 𝑅 = 8.314 𝑘𝐽/𝑘𝑚𝑜𝑙 𝐾
Molecular weight of 𝐻2 𝑂 = 18 𝑘𝑔 𝑘𝑚𝑜𝑙
∆𝐻 𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 = 2275 𝑘𝐽 𝑘𝑔 × 18 𝑘𝑔 𝑘𝑚𝑜𝑙
= 40,950 𝑘𝐽/𝑘𝑚𝑜𝑙
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Using Clasius-Clapeyron equation,
𝑃2𝑠𝑎𝑡 ∆𝐻𝑣𝑎𝑝𝑜𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 1 1
ln 𝑠𝑎𝑡 = −
𝑃1 𝑅 𝑇1 𝑇 2
101.3 40,950 𝑘𝐽/𝑘𝑚𝑜𝑙 1 1
ln 𝑠𝑎𝑡 = −
𝑃1 8.314 𝑘𝐽/𝑘𝑚𝑜𝑙 𝐾 363 373
101.3
ln 𝑠𝑎𝑡 = 0.36377
𝑃1
101.3 0.36377 = 1.4387
= 𝑒
𝑃1𝑠𝑎𝑡
𝑠𝑎𝑡
101.3
𝑃1 =
1.4387
𝑃1𝑠𝑎𝑡 = 70.41 𝑘𝑃𝑎

The vapour pressure of water at 363 𝐾 is 70.41 𝑘𝑃𝑎

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