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GMR Institute of Technology

Rajam, Andhra Pradesh


(An Autonomous Institution Affiliated to JNTUK, AP)

Department of Chemical Engineering


rd
Class 3 Sem. - B. Tech. (Chemical Engineering)
Course Chemical Process Calculations Course Code CHEM-2403
Prepared by Mr. P. Satya Sagar, Sr. Assistant Professor
Lecture Topic Vapor pressure plots
Course Outcome CCHEM203.2 Program Outcome PO1,PO13
Duration 50 min Lecture 7 of 45 Unit I
REMEMBER UNDERSTAND APPLY ANALYSE EVALUATE CREATE
Learning Level
(Tick whichever is applicable)

1. Objectives
a. To outline the usage of Vapor pressure plots
2. Topic Learning Outcomes: After the completion of the class the students will able to
a. Utilise the Vapor pressure plots and able to calculate vapor pressures of many compounds
3. Teaching Methodology
a. Chalk & Talk /PPT Mode
4. Applications:
a. Evaporation, drying , condensation, distillation , air conditioning , air separation ,
humidification and dehumidification
5. Evocation

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6. Discussion

Vapour-Pressure Plots :
From experimental data various types of plots have been devised for relating vapour
pressures to temperature. Use of an ordinary uniform scale of coordinates does not result in a
satisfactory plot because of the extreme curvature encountered. A single chart cannot be used
over a wide temperature range without sacrifice of accuracy at the lower temperatures, and the
rapidly changing slope makes both interpolation and extrapolation uncertain.

A better method which has been extensively used is to plot the logarithm of the vapour
pressure (log p) against the reciprocal of the absolute temperature (1/T). The resulting curves,
while not straight, show much less curvature than a rectangular plot and may be read accurately
over wide ranges of temperature. Another method is to plot the logarithm of the pressure against
temperature on a uniform scale. This method does not reduce the curvature of the vapour
pressure lines as much as the use of the reciprocal temperature scale but is easier to construct and
read.
As a means of
deriving consistent vapour
pressure data for homologous
series of closely related
compounds Coates and
Brown developed a special
method of plotting which has
proved particularly valuable
for the hydrocarbons. For this
plot rectangular coordinate
paper is used with
temperatures as abscissas and
normal boiling points as
ordinates. Curved lines of
constant vapour pressure are

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then plotted from the experimental data available for the various members of the series. This
method is particularly well adapted to extrapolating data obtained for the lowest boiling
homologs of a series in order to estimate vapour pressures of the higher boiling homologs.
Reference-Substance Plots :
The methods of plotting described above all result in lines having some degree of
curvature, which makes necessary a considerable number of experimental data for the complete
definition of the vapour-pressure curve. Where only limited data are available there is great
advantage to a method of plotting that yield straight lines over a range of conditions. With such a
method a complete curve can be established from only two experimental points and erratic data
can be detected. Where an accurate evaluation of a physical property has been developed over a
wide range of conditions for one substance the resulting relationship frequently may be made the
basis of empirical plots for other substances for not greatly different properties. This general
method may be applied to vapour-pressure data by selecting a reference substance the
temperature-vapour pressure relationship of which has been evaluated over a wide range. A
function of the temperature at which some other substance exhibits a given vapour pressure may
then be plotted against the same
function of temperature at which the
reference substance as the same
vapour pressure. Or, conversely, a
function of the vapour pressure of
the substance at a given temperature
may be plotted against the same
function of vapour pressure of the
reference substance at the same
temperature.
By proper selection of the
reference substance and the
functions of the properties plotted,
curves that approximate straight
lines over wide ranges of conditions

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are obtained. The best results are obtained with reference substances as similar as possible in
chemical structure and physical properties to the compounds of interest.

Equal-pressure rerefernce-substancePlots : The first reference-substance plot of vapour-


pressure data was proposed by Duhring, who plotted the temperature at which the substance of
interest as a given vapour-pressure against the temperature at which the reference substance has
the same vapour pressure. Duhring lines of Sodium hydroxide solutions are plotted in fig 17,page
104(Chemical Process Principles,part I) with water used as the reference substance. Each of
these lines relates the temperature of the designated solution to the temperature at which water
exerts the same vapour pressure. Vapour-pressure data for water appear in Table 5, page
82(Chemical Process Principles,partI).

Equal-temperature rerefernce-substancePlots: where the logarithm of the vapour


pressure of a substance is plotted against the logarithm of the vapour pressure of a reference
substance, both at the same temperature, a nearly straight line results. This method of plotting
was introduced by Cox and later fully discussed by Othmer. Cox found that a wide variety of
substances plotted as nearly straight lines by this method up to the critical point of the reference
substance.
Fig 15 (page84,Chemical Process Principles, partI ) is a Cox chart from which, for
simplicity in use, the logarithmic scale of pressures of the reference substance has been omitted
and only the auxiliary temperature scale derived from it shows. Such a chart may be constructed
by plotting vapour pressures as ordinates against reference-substance vapour pressures on multi
cycle double logarithmic paper. From the vapour-pressure data of the reference substance an
auxiliary abscissa scale of temperatures is established. To extend the range of the chart to
temperatures higher than the critical temperature of this reference substance a second higher-
boiling reference substance is selected and its vapour-pressure data are plotted over the
temperature range of the first reference substance. The vapour-pressure line of the second
reference substance is then extended, and from it the extension of the auxiliary temperature
abscissa scale is established. Fig 15 was developed in this manner water being used as the
primary reference substance and mercury for temperatures above the critical of water.

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The Cox method of plotting has been studied by Calingaert and Davis who found that the
data for widely varying types of materials yield lines with little curvature when plotted on such a
chart. Furthermore, it was found that the curves of groups of closely related compounds
converge at single points which are characteristic of the groups. For example, single points of
convergence were found for each of the following groups; the paraffin hydrocarbons, the
benzene mono halides, the alcohols, the silicon hydride series, and the metals. For a member of a
group of materials having convergent curves only one experimental point and the point of
convergence of the group are necessary to establish a complete curve.

Department of Chemical Engineering


Class 3rd Sem. - B. Tech. (Chemical Engineering)
Course Chemical Process Calculations
Prepared by Mr. P. Satya Sagar, Sr. Assistant Professor

7. Mind Map :

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8. Readings:

1. Hougen, Olaf A., and Kenneth M. Watson. "Chemical Process Principles-Part 1:


Material and Energy Blances." (1948).
2. Himmelblau, David Mautner, and James B. Riggs. Basic principles and calculations
in chemical engineering. FT Press, 2012.
3. Bhatt, B. I., and S. M. Vora. Stoichiometry:(si units). Tata McGraw-Hill Pub. Co.,
1996.
4. http://www.chemteam.info/GasLaw/Clasius-Clapeyron-Equation.html
9. Questions:
Understand:
1) What are reference substance plots? Discuss about equal-pressure. Reference substance
plots and equal-temperature, reference-substance plots giving examples.
Apply:
2) The vapour pressure of acetone is 200 mm Hg at 22.70C. Liquid acetone is kept in a
sealed ask at 22.70C, and the gas above the liquid contains air and acetone vapour at a
pressure of 960 mm Hg.
(a) Compute the partial pressure of acetone in the gas.
(b) Compute the partial pressure of N2and
(c) Compute the mole fraction of acetone in the gas.
(d) How would you determine the boiling point of the acetone, assuming a constant
total pressure of 960 mm Hg. State the assumptions made.

10. Key Words:


Cox charts,
Reference substance plots,
Equal-temperature

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