CHT131

(Chemical Engineering Calculations for

Technologists)

Textbook: Himmelblau, D.M.; Riggs, J.B., Principles

of Chemical Engineering, 7th ed., Pearson
Education Inc, 2005

Asso. Prof. Dima Franca T. Apao

Department of Chemical Engineering & Technology
MSU-Iligan Institute of Technology
 UNIT 3
Lesson 3:
Single Component Two-Phase
Systems (Vapor Pressure)
 PHASE DIAGRAMS
Properties of compounds can be displayed
through phase diagrams. Phase diagrams enable
us to view properties of two or more phases as
functions of temperature, pressure, specific
volume, concentration, etc.
Let us make water as our example. The
following phase diagram of water will also
similarly apply to all other pure substances.
 In the diagram, the three phases of
water can be seen. In the green region,
water exists as solid (ice), in blue region,
it exists as liquid and in orange region,
water exists as vapor. Usually, a vapor is
a gas below the critical point because it
can condense while the word “gas” is called
non-condensable gas and is above the
critical point or a gas in a process at
conditions under which it cannot
condense.

We can see three curves or boundaries between two phases.

The green curve is called the solid-liquid equilibrium curve or melting/fusion curve.
At any point in this curve, solid and liquid water exist in equilibrium. The orange
curve separates the solid water from vapor. This is called the solid-vapor equilibrium
curve or the sublimation/deposition curve. On the other hand, the blue curve is
called the liquid-vapor equilibrium curve or vaporization/condensation curve,
which separates the liquid from the vapor phase. All three curves meet a the triple
point, where all three phases exist in equilibrium.
 a b c d e

Imagine a vessel containing pure ice. In the diagram above, this water’s
state is at point a within the blue dashed line. If we heat the vessel,
the temperature of water will increase at constant atmospheric pressure. When
the temperature reaches point b, the ice now starts to melt. At this
point, we have both ice and liquid water. At point c , all the ice turned to liquid
 a b c d e

and if we continue heating until point d, the first drop of vapor is now formed.
At this point, the water is called saturated liquid whose temperature is called
bubble point or boiling point. At point e, the water is completely vaporized.
Here, the process from point a to c is called melting process and from c to e is
called vaporization process, both at constant pressure.
Some Important Terms:
•Sublimation is when the substance goes
directly from solid to the gas state.
•Deposition occurs when a substance goes
from a gas state to a solid state; it is the
reverse process of sublimation.
•Melting occurs when a substance goes from
a solid to a liquid state.
•Fusion is when a substance goes from a
liquid to a solid state, the reverse of melting.
•Vaporization (or evaporation) is when a
substance goes from a liquid to a gaseous
state.
•Condensation occurs when a substance goes from a gaseous to a liquid state, the
reverse of vaporization.
•Critical Point – the point in temperature and pressure on a phase diagram where
the liquid and gaseous phases of a substance merge together into a single phase.
Beyond the temperature of the critical point, the merged single phase is known as a
supercritical fluid.
•Triple Point occurs when both the temperature
and pressure of the three phases of the
substance coexist in equilibrium. At this point,
the three phases (soild, liquid, vapor) exist in
equilibrium.
•A liquid that is about to vaporize is called a
saturated liquid. Once boiling starts, the
temperature stops rising until the liquid is
completely vaporized. Any heat loss from this
vapor will cause some of the vapor to
condense. A vapor that is about to condense is
called a saturated vapor.
•The boiling point of a liquid varies according to the applied pressure; the normal boiling
point is the temperature at which the vapor pressure is equal to the standard sea-level
atmospheric pressure (760 mm [29.92 inches] of mercury). At sea level, water boils at
100° C (212° F).
•The bubble point/boiling point is the temperature at which the first drop of a liquid
begins to vaporize.
•The dew point is the temperature at which the first drop of a vapor begins to condense.
WATCH THESE VIDEOS (1)Phase diagrams: https://www.youtube.com/watch?v=zSwG59d8OCc
(2) Phase diagrams: https://www.youtube.com/watch?v=Xwm98B3gLPw
WATCH THIS VIDEO Evaporation, vapour pressure and boiling: https
://www.youtube.com/watch?v=CfagHzOtIDM
Vapor pressure is a measure of the tendency of a material to change
into the gaseous or vapor state, and it increases with temperature.
The temperature at which the vapor pressure at the surface of a
liquid becomes equal to the pressure exerted by the surroundings
(or the atmospheric pressure) is called the boiling point of the liquid.
If the atmospheric pressure is standard which is 1 atm, the boiling
point of the liquid is specifically called normal boiling point.
ADDITIONAL READING RESOURCE: Vapor Pressure: https://
www.chem.purdue.edu/gchelp/liquids/vpress.html

ESTIMATING VAPOR PRESSURES

As can be seen from the phase diagrams of water, vapor pressure
(P*) versus T is not a linear function. There are many empirical
equations that be used in estimating vapor pressure of pure
substances which have sufficient accuracy. One of these is the
Antoine’s equation which predicts P* from temperature.
ANTOINE EQUATION

The above table of constants A, B and C can be seen in Appendix G of our

textbook.
SAMPLE PROBLEMS
1. What is the saturation pressure of water at 312K ?
Solution:
Using Antoine’s equation:
From the Table, for water: A = 18.3036 ; B = 3816.44 ; C = -46.13
Substituting values:

ln(P*) = 3.949066
P* = inv ln (3.949066) or e3.949066

P* = 51.887 mm Hg (ANSWER)

Another method of estimating the vapor pressure for water is by the use of
steam tables. Steam tables display the thermodynamic properties (P, T, molar
volume, enthalpy, etc.) of liquid water and water vapor.
Some copies of our textbook have attachment of steam tables at the back or
right before the back cover, but other copies do not have.
Here is a portion of Steam table in SI unit:
For example, if we use the steam table method for example 1, we will find the
saturation pressure (second column in the given steam table) corresponding to the
given temperature which is 312oK. Take note that the saturation pressure is the
pressure when the liquid water becomes saturated (at bubble point, ready to
vaporize), which is equal to the vapour pressure.
ToC = 312oK – 273.15 = 38.85oC
From the steam table, here’s what we can get:
T(oC) Psat = P* (kPa)
35 5.6291
38.85 x=?
40 7.3851
To solve for P* at 38.85oC, we will use the method of interpolation. Recall that
interpolation method assumes linear relationship between the two variables, and
so it makes use of ratio and proportion approach.

Solving for x,
x = 6.9812 kPa
Thus, P* in mm Hg = (6.9812 kPa) (ANSWER)
This answer is close enough to the answer P*= 51.887 mm Hg when Antoine’s
equation was used.
2. What is the vapor pressure of acetone at 77oC?
Solution:
Using Antoine’s equation:
From the Table, for acetone: A = 16.6513 ; B = 2940.46 ; C = -35.93
Substituting values:

ln(P*) = 7.293334
P* = e7.293334

P* = 1470.465 mm Hg (ANSWER)
3. Calculate the normal boiling point of water.
Solution:
Liquid boils when its vapor pressure is equal to the atmospheric
pressure. The normal boiling point (NBP) occurs when the
atmospheric pressure is equal to the standard value which is 1 atm
or 760 mm Hg.
Using Antoine’s equation:
From the Table, for water: A = 18.3036 ; B = 3816.44 ; C = -46.13
Substituting values:

ln(760) =

Solving for TNBP:

TNBP = 373.15 oK or 100oC (ANSWER)
Problem 4, p. 497, 7th ed.
Determine the normal boiling point of benzene from Antoine
equation.
Solution:
Using Antoine’s equation:
From the Table, for benzene: A = 15.9008 ; B = 2788.51 ; C = -52.36
Substituting values:

ln(760) =

Solving for TNBP:

TNBP = 353.25 oK or 80.10oC (ANSWER)