• DECEMBER 2019

Phase Change and Enthalpy

Thermal Capacitance in Heat Transfer Analysis –

Lesson 4
 What is Phase Change?

• Matter exists in one of the three phases: solid, liquid or gas. The transition of matter
from one phase to another is known as a phase change.

Sublimation
Melting Boiling
Solid Liquid Gas
Solidification Condensation
Deposition
• Phase change generally occurs at a constant temperature when the pressure is
constant. This constant temperature has different names based on the process,
e.g., boiling point, melting point, etc.

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What is Phase Change?

Melting of butter when heated Melting of wax candle when lighted Boiling of water

Sublimation of Sublimation of dry ice Forming of morning dew due

naphthalene balls (solid carbon dioxide) to condensation

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How Does Phase Change Occur?

• Gases have more energy than liquids, and liquids have more energy than solids.
• When a material is heated, the energy of its molecules increases.
• As more heat energy is added to a solid material, at a certain temperature the molecules have
enough energy to overcome intermolecular forces, and transition to a liquid. This process is
known as melting and the temperature at which this process occurs is called the melting point.
• Further, if we keep adding heat, at a certain temperature the molecules in the liquid will have
enough energy to transition to a gas. This process is called boiling, and the transition
temperature is called the boiling point.

Energy
:
Solid < Liquid < Gas

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 Enthalpy

• The amount of energy required to change the phase of a material is known as the enthalpy, 𝐇 or latent heat
for that phase change. Its SI unit is joule.
• Heating a solid causes its molecules to vibrate more, thereby increasing the temperature of the solid (as
predicted by its specific heat).
• When the temperature of the solid reaches its melting point, adding more heat does not change the
temperature because all the heat goes into melting the solid. Thus, phase change generally occurs at a
constant temperature.
• Few exceptions exist, e.g., amorphous solids do not have ordered internal structure, and hence do not have a
sharp melting point. Temperature
Melting occurs Liquid phase
𝑇𝑚
Melting point Solid phase

Enthalpy

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 Enthalpy

• The amount of heat required to melt the solid completely is known as the enthalpy of melting or latent heat
of melting.
• The enthalpy of solidification is numerically equal to the enthalpy of melting. But the enthalpy of melting is
positive (heat is added to the system), while the enthalpy of solidification is negative (heat is removed from the
system).
• The temperature at which phase change occurs in a given material depends on the pressure.
• For example, water boils at 1000C at atmospheric pressure, but boils at 1200C in a pressure cooker due to
higher pressure. Thus, food cooks faster in a pressure cooker.

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 Simulating Phase Change

• Enthalpy is an additional material property that needs to be defined when simulating melting or solidification.
• Generally, in textbooks, enthalpy is defined as the energy absorbed or released by a body to undergo phase
change.
• But in simulations, this definition is modified to be the energy absorbed by a “unit volume” of a body (i.e. it
has dimensions of energy/volume).
• Enthalpy can be calculated from specific heat capacity, 𝑐, and density of material, ρ, using:

𝐻 = න ρ 𝑐 𝑇 𝑑𝑇

Enthalpy Liquid phase

• But for accuracy, we define an enthalpy curve.

Solid phase

𝑇𝑚 Temperature

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 Simulating Freezing of Water to Ice – Geometry

• Let us simulate the freezing of water to ice in a freezer. Let’s assume that the water is initially at 100C. The freezer is
maintained at a constant temperature of -50C. The freezing point of water is 00C.

Water

Plastic

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 Simulating Freezing of Water to Ice – Material Properties

Property Value
• We first need to define an enthalpy curve for water, using
the data on the right. Melting point 00C
Density 997 kg/m3
• Let’s say the enthalpy is 0 at
-100C. Instead of a distinct
melting point at 00C, let’s assume melting starts at -10C Solid specific heat (for ice), 𝑐𝑠 2108 J/kg-0C
and ends at 10C (to avoid abrupt, steep changes in Liquid specific heat (for water), 𝑐𝑙 4220 J/kg-0C
enthalpy). Enthalpy of melting, ∆𝐻𝑚 334000 J/kg

• 𝐻 𝑇=−10𝐶 = 𝐻 𝑇=−100𝐶 + ρ𝑐𝑠 ∆𝑇 = 0 + 997 × 2108 × 9 = 18915084 J/𝑚3 T (0C) H (J/m3)

• 𝐻 𝑇=10 𝐶 = 𝐻 𝑇=−10𝐶 + ρ∆𝐻𝑚 = 𝐻 𝑇=−10 𝐶 + 997 × 334000 = 351913084 J/𝑚3 -10 1e-5
-1 18915084
• 𝐻 𝑇=200𝐶 = 𝐻 𝑇=10𝐶 + ρ𝑐𝑙 ∆𝑇 = 𝐻 𝑇=10𝐶 + 997 × 4220 × 19 = 431852544 J/𝑚3
1 351913084
20 431852544

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Simulating Freezing of Water to Ice – Boundary Conditions

• The initial temperature of the water and the ice

tray is defined to be 100C.
• We define a step which is 10,000 s long (166.6
minutes). The convection boundary condition is
defined on the surfaces of the ice-tray and the
water that are in contact with the cold freezer
air. We assume a film coefficient of 30 W/m2∙0C.
The ambient temperature of the freezer is
assumed to be -50C.

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 Simulating freezing of water to ice – results

Temperature distribution at different times. Red = liquid, green = transition, blue = solid.

t = 100 s – Water is in a liquid phase t = 4210 s - Transition between liquid t = 6620 s (1 hr 50 min) - All water
and solid phase solidified into ice.

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 Simulating Freezing of Water to Ice – Results

If we plot the variation of average temperature of water with time, we find that the temperature remains almost
constant at 00C when the water undergoes freezing. Thus, heat removed from water during this time does not reduce
the temperature of the water but is in fact spent in transforming the water to ice.

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Applications of Melting and Solidification in Industry

Solder is melted and solidified quickly 3D printing involves depositing material in

to connect various electronic parts. liquid phase layer-by-layer, and allowing it to
cool down to form complex solid shapes.

Casting is a process in which molten metal in

liquid phase is poured in a mold and cooled to
get a solid body with the desired shape.

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