Chemical Engineering

Thermodynamics (CB206)

Chemical and Biochemical Engineering

Indian Institute of Technology Patna

Atanu K Metya
atanu.metya@iitp.ac.in
 Chemical Engineering Thermodynamics

Equations of State and Generalized Correlations

for Prediction of Volumetric Properties of Fluids
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• Phase Rule
•F=C–P+2
• F is the number of degrees of freedom, P is the number of phases, and C
is the number of chemical species present in the system

• How many phase-rule variables must be specified to fix the thermodynamic

state of each of the following systems?
• Liquid water in equilibrium with its vapor.
• Liquid water in equilibrium with a mixture of water vapor and nitrogen.
• A three-phase system of a saturated aqueous salt solution at its boiling
point with excess salt crystals present.
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Phase-change processes of pure substances

• Compressed liquid or a subcooled liquid

• Saturated liquid

• Saturated Vapor and Superheated Vapor

• Saturated liquid–vapor mixture

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• Saturation Temperature (Tsat): at a given pressure,

the temperature at which a pure substance changes
phase

• Saturation Pressure (Psat): at a given temperature,

the pressure at which a pure substance changes phase
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• Latent heat
• Latent heat of fusion
• Latent heat of vaporization
• At 1 atm. pressure, the latent heat of fusion of water is 333.7 kJ/kg and the
latent heat of vaporization is 2256.5 kJ/kg
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• Liquid–vapor saturation curve.

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The T-v Diagram for a pure

substance

• Critical point: the saturated

liquid and saturated vapor states
are identical
• The critical-point properties of
water are
• Pcr = 22.06 MPa,
• Tcr = 373.95°C
• vcr = 0.003106 m3/kg.
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• The T-v Diagram

• Saturated liquid line

• Saturated vapor line

• Compressed liquid region

• Superheated vapor region

• Saturated liquid–vapor mixture

region or the wet region
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• The P-v Diagram

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• PV diagrams for a pure substance
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PT Behavior of Pure
Substances
• Sublimation curve
• Fusion curve
• Vaporization curve
• Critical point
• Phase diagram
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Saturated Liquid and Saturated Vapor States
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Saturated Liquid and Saturated Vapor States
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Saturated Liquid and Saturated Vapor States

• A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine
the pressure in the tank and the volume of the tank.

• A piston–cylinder device contains 2 ft3 of saturated water vapor at 50-psia

pressure. Determine the temperature and the mass of the vapor inside the
cylinder.

• A mass of 200 g of saturated liquid water is completely vaporized at a

constant pressure of 100 kPa. Determine (a) the volume change and (b) the
amount of energy transferred to the water.
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• Saturated Liquid–Vapor Mixture

• Quality (x): the ratio of the mass of vapor to the total mass of the mixture
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• A rigid tank contains 10 kg of water at 90°C. If 8 kg of the water is in the

liquid form and the rest is in the vapor form, determine (a) the pressure in
the tank and (b) the volume of the tank.

• An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of 160 kPa.

Determine (a) the temperature, (b) the quality, (c) the enthalpy of the
refrigerant, and (d) the volume occupied by the vapor phase.
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• Properties of saturated ice–water vapor mixtures
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• Properties of saturated ice–water vapor mixtures
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Superheated Vapor
Compared to saturated vapor, superheated vapor is characterized by
• Lower pressures (P < Psat at a given T)
• Higher temperatures (T > Tsat at a given P)
• Higher specific volumes (v > vg at a given P or T)
• Higher internal energies (u > ug at a given P or T)
• Higher enthalpies (h > hg at a given P or T)
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• One pound-mass of water fills a 2.29-ft3 rigid container at an initial

pressure of 250 psia. The container is then cooled to 100°F. Determine the
initial temperature and final pressure of the water.

• Determine the temperature of water at a state of P = 0.5 MPa and h = 2890

kJ/kg.
 Chemical Engineering Thermodynamics

Compressed Liquid
• In the absence of compressed liquid data, treat compressed liquid as a
saturated liquid at the given temperature
• In general, a compressed liquid is characterized by
• Higher pressures (P > Psat at a given T)
• Lower temperatures (T < Tsat at a given P)
• Lower specific volumes (v < vf at a given P or T)
• Lower internal energies (u < uf at a given P or T)
• Lower enthalpies (h < hf at a given P or T)
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• Determine the internal energy of compressed liquid water at 80°C and 5

MPa, using (a) data from the compressed liquid table and (b) saturated
liquid data. What is the error involved in the second case?

• Determine the missing properties and the phase descriptions in the

following table for water:
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